WO2012091167A2 - Primer composition for silicone pressure-sensitive adhesive, laminate and silicone pressure-sensitive adhesive tape - Google Patents
Primer composition for silicone pressure-sensitive adhesive, laminate and silicone pressure-sensitive adhesive tape Download PDFInfo
- Publication number
- WO2012091167A2 WO2012091167A2 PCT/JP2011/080586 JP2011080586W WO2012091167A2 WO 2012091167 A2 WO2012091167 A2 WO 2012091167A2 JP 2011080586 W JP2011080586 W JP 2011080586W WO 2012091167 A2 WO2012091167 A2 WO 2012091167A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- silicone pressure
- sensitive adhesive
- average
- primer composition
- sheet
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
Abstract
Primer composition for silicone pressure-sensitive adhesives comprises (A) alkenyl-terminated diorganopolysiloxane represented by formula (1) R1R2
2SiO(R2
2SiO)pSiR2
2R1 (1), (B) an organohydrogenpolysiloxane represented by formula (2) (R3
3SiO1/2)k(R3HSiO2/2)m(R3
2SiO2/2)n(R3SiO3/2)p (2), and (C) a hydrosilylation reaction catalyst. Laminate comprises a sheet-form substrate, a primer layer provided by the cure on the sheet-form substrate of the primer composition, and a silicone pressure-sensitive adhesive layer formed on the primer layer. Silicone pressure-sensitive adhesive tape comprising the aforementioned laminate wherein the sheet-form substrate is a plastic film tape.
Description
DESCRIPTION
PRIMER COMPOSITION FOR SILICONE PRESSURE-SENSITIVE ADHESIVE, LAMINATE AND SILICONE PRESSURE-SENSITIVE ADHESIVE TAPE
Technical Field
[0001] The present invention relates to a primer composition for silicone pressure- sensitive adhesives, to a laminate, and to a silicone pressure-sensitive adhesive tape, and more particularly relates to a primer composition that can bring about strong adhesion between a silicone pressure-sensitive adhesive and a sheet-form substrate, e.g., a plastic film substrate, to a laminate comprising a silicone pressure-sensitive adhesive layer disposed on a sheet-form substrate with a cured layer from this primer composition interposed therebetween, and to a silicone pressure-sensitive adhesive tape comprising a silicone pressure-sensitive adhesive layer disposed on a plastic tape with a cured layer from this primer composition interposed therebetween.
Background Art
[0002] Silicone pressure-sensitive adhesive compositions characteristically exhibit a better pressure-sensitive adhesiveness to a variety of adherends, better electrical insulating properties, a better heat resistance, and a better cold resistance than organic pressure- sensitive adhesive compositions such as acrylic systems, organic rubber systems, and so forth, and for these reasons are used for applications such as heat-resistant tapes, electrical insulating tapes, heat-seal tapes, masking tapes for metal plating, and so forth. When these pressure-sensitive adhesive tapes are wound into the usual roll configuration and then forcefully unwound for use, the silicone pressure-sensitive adhesive layer can separate from the sheet-form substrate, for example, from the plastic film. In addition, when the pressure-sensitive adhesive tape is cut, only the plastic film substrate may undergo scission and the silicone pressure-sensitive adhesive layer may then lift up off the plastic film substrate and/or cutting may occur with the silicone pressure-sensitive adhesive layer undergoing extension like a fiber being drawn.
[0003] A method in which a primer is preliminarily applied to the sheet-form substrate may be adopted when the silicone pressure-sensitive adhesive does not exhibit sufficient adhesiveness to a sheet-form substrate, e.g., a plastic film. The primer composition proposed for such a primer in JP 06-039584 B (Patent Reference 1) comprises (a) a diorganopolysiloxane given by the general formula
wherein R represents a substituted or unsubstituted monovalent hydrocarbyl group and "n" is an integer greater than or equal to 30; (b) an organohydrogenpolysiloxane that has in each molecule at least three hydrogen atoms bonded to silicon and has substituted or unsubstituted monovalent hydrocarbyl groups as its organic groups; (c) a vinyl and/or acrylic copolymer that contains a hydrolyzable silyl group; and (d) a metal salt of an organic carboxylic acid.
[0004] The primer composition for silicone pressure-sensitive adhesives proposed in JP 2002-338890 A (Patent Reference 2) characteristically comprises (A) a
diorganopolysiloxane having an average degree of polymerization of 500 to 2,000 and containing an alkenyl group at both molecular chain terminals, wherein the number of moles of the alkenyl contained therein is 0.001 to 0.005 mole per 100 g of this
diorganopolysiloxane; (B) an organohydrogenpolysiloxane that contains at least two hydrogen atoms directly bonded to silicon in each molecule; (C) a platinum-based curing catalyst; and (D) a reaction inhibitor.
The primer compositions disclosed in its examples and elsewhere comprise a dimethylpolysiloxane having a degree of polymerization of about 450 to 1 ,300 and having the vinyl group at both molecular chain terminals and a vinyl group content of 0.002 to 0.003 mole/100 g, an organohydrogenpolysiloxane, a platinum-based curing catalyst, and an addition reaction inhibitor. However, with respect to the organohydrogenpolysiloxane, only a hydrogen content of 1.55 mole/100 g is disclosed and there is no disclosure at all with regard to the organic groups, chemical structure, degree of polymerization, and viscosity of this organohydrogenpolysiloxane.
[0005] The silicone pressure-sensitive adhesive tape disclosed in JP 2010-184953 A (Patent Reference 3) is characteristically provided by laminating a plastic film substrate on a silicone pressure-sensitive adhesive layer formed on a separator for application with silicone pressure-sensitive adhesives, wherein a cured layer from an addition-curable primer composition comprising the following components (A) to (D) and intended for application with silicone pressure-sensitive adhesives, is interposed between the plastic film substrate and the silicone pressure-sensitive adhesive layer:
(A) a diorganopolysiloxane that has an alkenyl group at both molecular chain terminals, an average degree of polymerization of from at least 100 to not more than 1,000, and an alkenyl group content of from at least 0.125 mole% to not more than 2.5 mol%,
(B) an organohydrogenpolysiloxane that has at least two hydrogen atoms directly bonded to silicon in each molecule,
(C) a platinum-based curing catalyst, and
(D) a reaction inhibitor.
The Specification discloses the following for component (B): a
methylhydrogenpolysiloxane endblocked by the trimethylsiloxy group at both molecular chain terminals which is represented by formula: (CH3)3SiO-[(CH3)HSiO]40-Si(CH3)3 etc., a methylhydrogensiloxane · dimethylsiloxane copolymer endblocked by the
trimethylsiloxy group at both molecular chain terminals which is represented by formula: (CH3)3SiO-[(CH3)HSiO]45-[(CH3)2SiO1] 15-Si(CH3)3 etc., and a branched
methylhydrogenpolysiloxane.
[0006]
[Patent Reference 1] JP 06-039584 B
[Patent Reference 2] JP 2002-338890 A
[Patent Reference 3] JP 2010-184953 A
Disclosure of Invention
Technical Problems to be Solved
[0007] However, the inventors noted that the adhesiveness of silicone pressure-sensitive adhesives to various sheet-form substrates, and particularly to plastic film substrates, could not be adequately improved even using the primer compositions described above. A particular problem was found to be the poor adhesiveness of silicone pressure-sensitive adhesives to heat-resistant plastic film substrates, such as highly heat-resistant polyester films and polyimide films.
In view of the problems described above, an object of the present invention is to provide a primer composition for use with silicone pressure-sensitive adhesives that, when a silicone pressure-sensitive adhesive is applied to a substrate and particularly to a sheet- form substrate such as a plastic film substrate, can provide a stronger adhesion between the silicone pressure-sensitive adhesive and the sheet-form substrate. A further object of the present invention is to provide a laminate in which a silicone pressure-sensitive adhesive is strongly adhered to a sheet-form substrate. A further object of the present invention is to provide a silicone pressure-sensitive adhesive tape in which a silicone pressure-sensitive adhesive is strongly adhered to a plastic film tape.
Solution to Problems
[0008] As a result of intensive and extensive investigations in order to achieve the objects listed above, the present inventors discovered that the problems described above could be solved by a primer composition for application with silicone pressure-sensitive adhesives, wherein the primer composition comprises a diorganopolysiloxane having an alkenyl group at both molecular chain terminals and having an average degree of polymerization of 400 to 2,000, an organohydrogenpolysiloxane having an average degree of polymerization of about 100 to 500 and having a high content of the
H 3 organohydrogensiloxane unit represented by the formula R3 HSiO2/2 (D unit) wherein R is a C1- 10 monovalent hydrocarbyl group or monovalent halogenated hydrocarbyl group that does not have an aliphatically unsaturated bond, and a hydrosilylation reaction catalyst. The present invention was achieved based on this discovery.
[0009] Thus, the problems described above can be solved by a primer composition for silicone pressure-sensitive adhesives, wherein the primer composition comprises the following components (A), (B), and (C):
(A) a diorganopolysiloxane having alkenyl groups at both molecular chain terminals and represented by the following average structural formula (1)
R 1 R22 SiO(R2 2SiO)pS iR2 2R 1 (1) wherein
R1 is a C2- 10 alkenyl group,
2
R is a C1- 10 monovalent hydrocarbyl group or monovalent halogenated hydrocarbyl group that does not contain an aliphatically unsaturated bond, and P + 2 is a number that on average is in the range from 400 to 2,000;
(B) an organohydrogenpolysiloxane represented by the following average compositional formula (2)
(R33 SiO 1 /2)k(R3 HSiO2/2)m(R32Si02 /2)n(R3 SiO3/2)p (2) wherein R3 is a C1- 10 monovalent hydrocarbyl group or monovalent halogenated hydrocarbyl group that does not have an aliphatically unsaturated bond,
"k" is a number that on average is (2 + p),
"m" is a number that on average is in the range from 100 to 500,
"n" and "p" are each numbers that on average are greater than or equal to 0, and
"m", "n", and "p" are numbers that on average are in ranges that satisfy the relationships 100≤ m + n + p≤ 500 and 0.8≤ m/(m + n + p)≤ 1 ; and
(C) a hydrosilylation reaction catalyst.
[0010] Moreover, the previously described problems can be even more favorably solved by a primer composition for silicone pressure-sensitive adhesives, wherein the
aforementioned component (A) is a diorganopolysiloxane having alkenyl groups at both molecular chain terminals and having an average value of 450 to 1 ,500 for P + 2 in formula (1) and the aforementioned component (B) is a straight-chain
organohydrogenpolysiloxane given by the average structural formula (3) below.
R33 S iO(R3 HSiO2/2)m l (R32S iO2/2)n l SiR33 (3)
3
wherein R is a C1- 10 monovalent hydrocarbyl group or monovalent halogenated hydrocarbyl group that does not have an aliphatically unsaturated bond,
"ml " is a number that on average is in the range from 100 to 500,
"nl " is a number that on average is greater than or equal to 0, and
ml and nl are numbers that on average are in ranges that satisfy the relationships 100≤ ml + nl≤ 500 and 0.9≤ ml/(ml + nl)≤ 1.
[0011] Because a primer layer provided by the cure of the aforementioned primer composition for silicone pressure-sensitive adhesives can bring about strong adhesion by silicone pressure-sensitive adhesives even to sheet-form substrates that have been difficult to adhesion with silicone pressure-sensitive adhesives, such as polyester films and polyimide films, the previously described problems can be thoroughly solved with a laminate comprising a sheet-form substrate, a primer layer that is provided by the cure on the sheet-form substrate of a primer composition for silicone pressure-sensitive adhesives, and a silicone pressure-sensitive adhesive layer formed on the primer layer, and a silicone pressure-sensitive adhesive tape comprising the aforementioned laminate wherein the sheet-form substrate is a plastic film tape.
Advantageous Effects of Invention
[0012] The primer composition for silicone pressure-sensitive adhesives of the present invention can, when a silicone pressure-sensitive adhesive, particularly a hydrosilylation reaction-curable silicone pressure-sensitive adhesive or an organoperoxide-curable silicone pressure-sensitive adhesive is applied to a sheet-form substrate, particularly a plastic film substrate, more particularly heat-resistant plastic film substrate, provide a stronger
adhesion between the silicone pressure-sensitive adhesive and the sheet-form substrate. In the laminate of the present invention, the silicone pressure-sensitive adhesive, particularly a hydrosilylation reaction-curing silicone pressure-sensitive adhesive or an
organoperoxide-curing silicone pressure-sensitive adhesive is strongly adhered to a sheet- form substrate, particularly a plastic film substrate, more particularly heat-resistant plastic film substrate.
In the adhesive tape of the present invention, the silicone pressure-sensitive adhesive, particularly a hydrosilylation reaction-curing silicone pressure-sensitive adhesive or an organoperoxide-curing silicone pressure-sensitive adhesive is strongly adhered to a plastic film tape, particularly a heat-resistant plastic film tape.
Description of the Invention
[0013] The primer composition for silicone pressure-sensitive adhesives of the present invention will be described in detail first. The primer composition for silicone pressure- sensitive adhesive according to the present invention functions to substantially improve the adhesiveness between a silicone pressure-sensitive adhesive and a sheet-form substrate and comprises the following components (A), (B), and (C):
(A) a diorganopolysiloxane having alkenyl groups at both molecular chain terminals and represented by the following average structural formula (1)
R 1 R22 SiO(R2 2 SiO)pSiR2 2R 1 (1) wherein
. 1 .
R is a C2- 10 alkenyl group,
2
R is a C1- 10 monovalent hydrocarbyl group or monovalent halogenated hydrocarbyl group that does not contain an aliphatically unsaturated bond, and P + 2 is a number that on average is in the range from 400 to 2,000;
(B) an organohydrogenpolysiloxane represented by the following average compositional formula (2)
(R33 SiO 1 /2)k(R3 HSiO2 /2)m(R3 2SiO2 /2)n(R3 SiO3 /2)p (2)
3
wherein R is a C1- 10 monovalent hydrocarbyl group or monovalent halogenated hydrocarbyl group that does not have an aliphatically unsaturated bond,
"k" is a number that on average is (2 + p),
"m" is a number that on average is in the range from 100 to 500,
"n" and "p" are each numbers that on average are greater than or equal to 0, and "m", "n", and "p" are numbers that on average are in ranges that satisfy the relationships 100≤m + n + p≤ 500 and 0.8≤ m/(m + n + p)≤ 1 ; and
(C) a hydrosilylation reaction catalyst.
[0014] Component (A) is the base component of the primer composition of the present invention and undergoes curing by crosslinking through a hydrosilylation reaction with component (B) under the catalytic effect of component (C). Component (A) is a straight- chain diorganopolysiloxane that has alkenyl groups at both molecular chain terminals and represented by the preceding average structural formula (1). Because component (A) has a certain long molecular chain length and has alkenyl groups only at the two molecular chain terminals, it has a low alkenyl group content and a side chain-to-side chain hydrosilylation reaction does not occur, therefore, its use in combination with the component (B) described below, can substantially improve the adhesiveness between a silicone pressure-sensitive adhesive and a sheet-form substrate.
[0015] R1 in the formula (1) is a C2- 1 0 alkenyl group and is preferably a C2-6 alkenyl group and can be specifically exemplified by vinyl, allyl, butenyl, and hexenyl. Vinyl and hexenyl are particularly preferred thereamong from the standpoint of easiness of production.
[0016] R2 is a C1- 10 monovalent hydrocarbyl group or monovalent halogenated hydrocarbyl group that does not have an aliphatically unsaturated bond, and the C1- 10 monovalent hydrocarbyl group can be exemplified by alkyl groups, e.g., methyl, ethyl, propyl, pentyl, and octyl; alicyclic groups, e.g., cyclohexyl; and aryl groups, e.g., phenyl, tolyl, xylyl, benzyl, α -methylstyryl, and 2-phenylethyl.
The C1- 10 monovalent halogenated hydrocarbyl group can be exemplified by monovalent fluorinated hydrocarbyl groups, particularly, perfluoroalkyl groups such as 3,3,3-trifluoropropyl and 4,4,4-3, 3-pentafluorobutyl, and by monovalent chlorinated hydrocarbyl groups, particularly, chloroalkyl group such as 3-chloropropyl and
chlorophenyl group such as dichlorophenyl.
2 .
From an industrial standpoint, all of the R in the molecule is preferably only a Cj _
10 alkyl group wherein at least 50 % by mole thereof is methyl, or only methyl group and
phenyl group wherein at least 50 % by mole thereof is methyl, and particularly, only methyl group.
1 2
When R is vinyl and R is methyl in the average structural formula (1), the average structural formula (1) becomes the following average structural formula (1 -1)
ViMe2 SiO(Me2 S iO)pS iMe2Vi (1 -1) wherein Vi is vinyl, Me is methyl, and P + 2 is a number that on average is in the range from 400 to 2,000.
[0017] "P" denotes the number of diorganosiloxane units represented by the formula 2
R 2S1O2/2, and tne total number of siloxane units, which is represented by "P + 2", must on average be in the range from 400 to 2,000, is preferably on average in the range from 450 to 1 ,500, and is particularly preferably on average in the range from 700 to 1 ,300.
When "P + 2" is on average less than 400, the cured product from the primer composition will tend to exfoliate from the substrate surface and the effect as a primer is then not obtained to a satisfactory degree.
When "P + 2" is on average from at least 400 to not more than 2,000, exfoliation of the cured primer composition does not occur and the adhesiveness-improving effect i.e., priming effect (hereinafter called adhesiveness-improving effect) is obtained. The adhesiveness-improving effect becomes even more significant when "P + 2" is on average from at least 450 and particularly from at least 700 to not more than 2,000.
When, on the other hand, "P + 2" is on average more than 2,000, the adhesiveness between the silicone pressure-sensitive adhesive and the sheet-form substrate drops off and a trend of a declining adhesiveness-improving effect appears.
Total number of siloxane units is nearly equal to average polymerization degree. The average polymerization degree can be calculated from the weight average molecular weight obtained on the basis of calibration curve prepared from a standard polystyrene in GPC (gel permeation chromatography).
[0018] The alkenyl group content in component (A) is preferably 0.001 to 0.010 mole/100 g and particularly preferably is 0.002 to 0.006 mole/100 g.
[0019] Component (B) is a crosslinking agent for component (A) and is a component that is a characteristic feature of the present invention. Crosslinking occurs by its hydrosilylation reaction with component (A) under the catalytic effect of component (C).
Component (B) is a straight-chain or branched-chain organohydrogenpolysiloxane. The use of component (B) in combination with the previously described component (A)
results in a substantial increase in the adhesiveness between a silicone pressure-sensitive adhesive layer, particularly hydrosilylation reaction-curing silicone pressure-sensitive adhesive layer or an organoperoxide-curing silicone pressure-sensitive adhesive layer and its sheet-like substrate, preferably a plastic film substrate, more preferably a heat- resistant plastic film substrate. This occurs because, among the total siloxane units in component (B), the number of organohydrogensiloxane units which forms a straight- chain structure is on average in the range from 100 to 500, the sum of the number each of organohydrogensiloxane units-and diorganosiloxane units which form a straight-chain structure, and the number of monoorganosiloxane units which are branching units, is on average in the range from 100 to 500, and because component (B) has a large number of silicon-bonded hydrogen atoms in side chain position on the straight-chain structures.
[0020] In the organohydrogenpolysiloxane given by the average compositional formula 3
(2), R 3S1O 1 /2 is a triorganosiloxy unit (M unit), which is a structural unit for the
3 H
molecular chain terminal; R HS1O2/2 is an organohydrogensiloxy unit (D unit), which is
3
a siloxane chain structural unit; R 2S1O2/2 is an diorganosiloxy unit (D unit), which is a
3
siloxane chain structural unit; and R S1O3/2 is an organosiloxy unit (T unit), which is a branching unit.
3
[0021] R is a C1- 10 monovalent hydrocarbyl group or monovalent halogenated hydrocarbyl group that does not have an aliphatically unsaturated bond and can be exemplified by the same monovalent hydrocarbyl groups as for R1 above.
3
From an industrial standpoint, all of the R in the molecule is preferably only a C1- 10 alkyl group wherein at least 50 % by mole thereof is methyl, or only methyl group and phenyl group wherein at least 50 % by mole thereof is methyl, and particularly, only methyl group.
3
When R is methyl in the average structural formula (2), the average structural formula (2) becomes the following average structural formula (2-1)
(Me3 S1O 1 /2 )k(MeHS i02/2)m(Me2 S1O 1 /2 )n(MeS1O 3 /2 )p (2-1) wherein
Me is methyl,
"k" is a number that on average is (2 + p),
"m" is a number that on average is in the range from 100 to 500,
"n" and "p" are each numbers that on average are greater than or equal to 0, and "m", "n", and "p" are numbers that on average are in ranges that satisfy the relationships 100≤ m + n + p≤ 500 and 0.8≤ m/(m + n + p)≤ 1
[0022]
When p is 0 in the average structural formula (2), the organohydrogenpolysiloxane has a straight-chain structure, and the average structural formula (2) becomes the following average structural formula (2-2)
R3 3 S i0 1 /2 (R3HSiO1/2)m(R32 SiO2/2)nSi R3 3 (2-2)
3
wherein R 3 is the same group as described above,
"m" is a number that on average is in the range from 100 to 500,
"n" is numbers that on average are greater than or equal to 0, and
"m" and "n" are numbers that on average are in ranges that satisfy the relationships
100≤ m + n≤ 500 and 0.8≤ m/(m + n)≤ 1.
3
When R is methyl in the average structural formula (2-2), the average structural formula (2-2) becomes the following average structural formula (2-2-1 )
Me 3 SiO 1 /2 (Me HSiO2/2)m(Me 2 S i02 /2)nSi Me 3 (2-2-1) wherein Me is methyl, "m" and "n" are defined as above.
[0023] When m and (m + n + p) are on average less than 100, the adhesiveness between the silicone pressure-sensitive adhesive and sheet-form substrate is reduced and the adhesiveness-improving effect is diminished. When (m + n + p) is on average greater than 500, the organohydrogenpolysiloxane itself has a distinct tendency to gel and its production is problematic. It is particularly necessary here that m and (m + n + p) be on average at least 100. Even when using an organohydrogenpolysiloxane that satisfies the relationship 0.8≤ m/(m + n + p)≤ 1, an adequate adhesiveness-improving effect cannot be realized at m that is on average around 90, and (m + n + p) that is on average around 90.
[0024] When m/(m + n + p) is outside the range given above, i.e., is < 0.8, the organohydrogensiloxy unit (D unit) content in the molecule is inadequate and the cured
product from the primer composition will exfoliate from the sheet-form substrate surface and particularly from the surface of plastic film substrate and as a consequence the adhesiveness by the silicone pressure-sensitive adhesive to the sheet-form substrate will deteriorate and little adhesiveness-improving effect is exhibited.
Viewed from the perspective of the improvement in the adhesiveness between the silicone pressure-sensitive adhesive layer and a sheet-form substrate, "m" is on average preferably 100≤ m≤ 430, and more preferably 100≤ m≤ 400, "m", "n", and "p" preferably satisfy the relationship 0.90≤ m/(m + n + p)≤ 1.0 and more preferably satisfy the relationship 0.95≤ m/(m + n + p)≤ 1.0, and most preferably satisfy the relationship m/(m + n + p)=l .
[0025] There are no particular limitations on "k", "m", "n", and "p" as long as the previously described relationships are satisfied; however, viewed from the perspective of the adhesiveness-improving effect, component (B) preferably has a straight-chain or lightly branched chain structure in which the molecular chain is composed mainly of the
3
DH unit and "p", which indicates the number of R S1O3/2 units (T units) in average compositional formula (2), is preferably 0 or 1. "k" is 2 when "p" is 0, and is 3 when "p" is 1.
When "p" is 1 or 0, "m" is on average preferably 100≤ m≤ 430, and more preferably 100 ≤ m≤ 400, and "m" and "n" satisfy preferably the relationships 0.90≤ m/(m + n + p)≤1 ,≤ more preferably the relationship 0.95≤ m/( m + n + p)≤1 , and most preferably "n" is 0.
[0026] p = 0 is optimal from the standpoint of the adhesiveness-improving effect, and component (B) is most preferably a straight-chain organohydrogenpolysiloxane with the following formula (3)
R33 SiO(R3 HSiO2/2)m l (R32SiO2/2)n l S iR33 (3)
3
wherein R is the same group as described above,
"ml " is a number that on average is in the range from 100 to 500,
"nl " is a number that on average is greater than or equal to 0, and
"ml " and "nl " are numbers in ranges that satisfy the relationships 100≤ ml + nl≤ 500 and 0.9≤ ml /(ml + nl)≤ 1.
From the standpoint of the adhesiveness-improving effect, "ml " is preferably 100≤ ml≤ 430, and more preferably 100≤ ml≤ 400, and "ml " and "nl " satisfy preferably the relationships 0.90≤ ml/(ml + nl)≤1, more preferably the relationship 0.95≤ ml/(ml + nl)≤1 , and most preferably the relationship ml/(ml + nl) =1.
When nl is 0 in the average structural formula (3), the average structural formula becomes the average structural formula (3-1).
R33 SiO(R3 HSiO2/2)m l SiR33 (3-1)
3
wherein R is the same group as described above, and ml is the same number defined as above.
[0027] With regard to the amounts of incorporation of components (A) and (B), these are desirably incorporated so as to provide a ratio between the total number of moles of hydrogen atoms directly bonded to silicon in component (B) and the number of moles of alkenyl groups in component (A) (referred to below as H/Vi) of from 1 to 50, and from the standpoint of the adhesiveness-improving effect are more desirably incorporated so as to provide an H/Vi of from at least 8 to not more than 20 and are even more desirably incorporated so as to provide an H/Vi of from at least 10 to not more than 15. When the H/Vi is less than 1, the cured primer composition may not adequately adhere to a sheet- form substrate; when H/Vi is greater than 50, the adhesiveness of the cured primer composition may deteriorate with elapsed time.
[0028] The component (C) platinum-based curing catalyst accelerates the addition reaction between the alkenyl in component (A) and the silicon-bonded hydrogen in component (B). This hydrosilylation reaction-accelerating catalyst can be exemplified by chloroplatinic acid, alcohol solutions of chloroplatinic acid, chloroplatinic acid/olefin complexes, chloroplatinic acid/vinylsiloxane complexes, chloroplatinic acid/ketone complexes, platinum supported on silica powder, and platinum black.
Component (C) is incorporated in a catalytic amount, but its amount of
incorporation is not otherwise particularly limited. Component (C) is preferably
incorporated in an amount that provides from 1 to 1 ,000 ppm platinum metal with reference to the total amount of components (A) and (B). Curing becomes unsatisfactory at less than 1 ppm, while the composition can have a short pot life at more than 1,000 ppm. The use of more than 1 ,000 ppm is also economically disadvantageous due to the high cost of the platinum-type catalyst.
[0029] In addition to the previously described components, the primer composition for silicone pressure-sensitive adhesives of the present invention preferably contains an hydrosilylation reaction inhibitor in order to improve the storage stability at room temperature. This hydrosilylation reaction inhibitor can be specifically exemplified by alkynyl alcohols such as 3 -methyl- l -butyn-3-ol, 3,5-dimethyl-l-hexyn-3-ol, 3-methyl-l -
pentyn-3-ol, phenylbutynol, and 1 -ethynyl-l -cyclohexanol; ene-yne compounds such as 3-methyl-3-penten-l-yne, 3-methyl-3-hexen-l-yne and 3,5-dimethyl-3-hexen-l -yne; as well as benzotriazole, cyclic methylvinylsiloxanes, benzyl alcohol, and maleates and fumarates, for example, the well known dialkyl maleates, dialkenyl maleates,
dialkoxyalkyl fumarates, dialkyl fumarates, and dialkenyl fumarates. This addition reaction inhibitor is generally incorporated in the range from 0.001 to 5 weight parts per 100 weight parts for the total amount of components (A) and (B).
[0030] An organic solvent is preferably added to enable the thin and uniform coating of the primer composition for silicone pressure-sensitive adhesives of the present invention on the substrate. The type and quantity of incorporation of this organic solvent is adjusted considering such factors as the workability of the coating operation. The organic solvent can be exemplified by aromatic hydrocarbon solvents such as toluene, xylene, and benzene; aliphatic hydrocarbon solvents such as heptane, hexane, octane, and isoparaffin; ester solvents such as ethyl acetate and isobutyl acetate; ether solvents such as diisopropyl ether and 1 ,4-dioxane; as well as chlorinated aliphatic hydrocarbon solvents such as trichloroethylene, perchloroethylene, methylene chloride, and solvent volatile oils. Two or more organic solvents may be combined in view of, for example, the wettability by the primer composition on the substrate.
The organic solvent is incorporated in a quantity that enables the mixture of components (A) to (C) to be thinly and uniformly coated on the surface of the substrate, for example, 100 to 3000 mass parts per 100 mass parts for the sum of components (A) and (B).
[0031] The primer composition for silicone pressure-sensitive adhesives of the present invention has the previously described components (A) to (C) as its essential components, but may incorporate, for the purpose of achieving additional improvements in the adhesiveness to substrate, a trialkoxysilane that has at least one epoxy-functional organic group bonded directly to silicon in each molecule or an organooligosiloxane that has at least one epoxy-functional organic group bonded directly to silicon and at least three alkoxy groups bonded directly to silicon in each molecule. Combinations of two or more of these epoxy-functional organic group-containing trialkoxysilanes and these epoxy- functional organic group-containing organooligosiloxanes may be incorporated, but the total quantity of incorporation for this component is not more than 10 parts and
particularly preferably not more than 2 parts, in each case with reference to 100 parts for the total amount of components (A) and (B). The incorporation of more than 10 parts is disadvantageous for the cure of the primer composition. Other additives such as coloring
agents can be incorporated in a small amount as long as advantageous effects of the primer composition are not hindered.
[0032] The method of producing the primer composition for silicone pressure-sensitive adhesives of the present invention is not particularly limited. Component (A), component (B), and the optional organic solvent may first be mixed to uniformity. A hydrosilylation reaction inhibitor is then preferably admixed into the resulting mixture. As necessary, the previously described epoxy-functional organic group-containing trialkoxysilane or organooligosiloxane is admixed. Component (C) is preferably admixed either last or immediately prior to primer composition use.
[0033] The primer composition for silicone pressure-sensitive adhesives of the present invention is used to treat a sheet-form substrate surface in order to provide an excellent adhesiveness between the sheet-form substrate and the silicone adhesive layer. However, in order to achieve additional improvements in the adhesiveness, a surface-treated sheet- form substrate may be used as the sheet-form substrate to be coated with the primer composition for silicone pressure-sensitive adhesives; this surface treatment can be exemplified by treatment with another primer, corona discharge treatment, etching treatment, plasma treatment, and so forth.
[0034] The primer composition for silicone pressure-sensitive adhesives of the present invention is cured by leaving at room temperature, air drying, hot air drying, or heating after it has been uniformly coated on the sheet-form substrate. The coating rate should be an amount sufficient to bring about the formation of a thin primer film on the surface of the sheet-form substrate, for example, approximately 0.05 to 2.0 g/m2.
The application of a large amount is disfavored because this has the reverse effect of impairing the adhesiveness between the sheet-form substrate and the silicone adhesive. The thermosetting temperature and time will also vary as a function of the type of sheet- form substrate and the coating rate, but preferably may be selected as appropriate from the range of 80 to 180°C for 120 to 15 seconds.
[0035] The sheet-form substrate is, for example, a plastic film substrate, polyolefin- laminated paper, or metal foil, wherein a plastic film substrate is preferred and a heat- resistant plastic film substrate is particularly preferred.
The resin in the plastic film can be exemplified by heat-resistant resins comprising polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate (PEN); polyimide resins, polyimide ether resins, polyamideimide (PAI) resins, polyetheretherketone (PEEK) resins, liquid-crystal polyarylate resins,
polyethersulfone (PES) resins, and polyphenylene sulfide resins; general-purpose thermoplastic resins such as ABC resins, polyamide resins, polycarbonate resins, polystyrene resins, polypropylene resins, polyethylene resins, and polyvinyl chloride resins; and thermosetting resins such as epoxy resins and phenolic resins. Laminated films, as provided by laminating a plurality of plastic films from among the preceding, are a further example.
[0036] A known silicone pressure-sensitive adhesive can be used for the silicone pressure-sensitive adhesive that is applied to the sheet-form substrate, for example, an organoperoxide-curable silicone pressure-sensitive adhesive, which is cured under the effect of an organoperoxide, i.e., organic peroxide or a hydrosilylation reaction-curable silicone pressure-sensitive adhesive, which is cured under the effect of a hydrosilylation reaction catalyst or a condensation reaction-curable silicone pressure-sensitive adhesive.
The primer composition for silicone pressure-sensitive adhesives of the present invention is effectively used even with hydrosilylation reaction-curable silicone pressure- sensitive adhesives having a low crosslink density, which are regarded as having a generally poor adhesiveness to substrates and with organoperoxide-curable silicone pressure-sensitive adhesives, which are regarded as having a better adhesiveness to sheet- form substrates than hydrosilylation reaction-curable silicone pressure-sensitive adhesives.
"silicone pressure sensitive adhesive" is meant an adhesive comprising one or more siloxane components possessing sufficient tackiness and cohesive strength so that it can be adhered with mild pressure to a clean substrate and then usually can be ripped therefrom if necessary, and it generally comprises a crosslinkable diorganopolysiloxane, an
organopolysiloxane resin comprising triorganosiloxy units and SiO4/2 units, and a curing agent, or comprises a condensation product of a diorganopolysiloxane and an
organopolysiloxane resin comprising triorganosiloxy units and SiO4/2 units, and a curing agent as explained for example in US Patent No.5,300,171 and US Patent No.4,591,622.
Organoperoxide-curable silicone pressure-sensitive adhesives usually contain vinyl-containing diorganopolysiloxane and cure by the action of an organoperoxide at elevated temperatures.
Hydrosilylation reaction-curable silicone pressure-sensitive adhesive cure under hydrosilylation reaction usually between vinyl groups of a diorganopolysiloxane etc. and SiH groups of an organohydrogenpolysiloxane by the action of a platinum-based catalyst.
Condensation reaction-curable silicone pressure-sensitive adhesives cure under condensation reaction usually between silanol groups or hydrolysable groups of a diorganopolysiloxane etc. by the action of a condensation catalyst.
[0037] The primer composition for silicone pressure-sensitive adhesives according to the present invention is useful for producing a laminate that is provided with (i) a primer layer on a sheet-form substrate, the primer layer having been formed as described above by the cure of the primer composition for silicone pressure-sensitive adhesives, and (ii) a silicone pressure-sensitive adhesive layer formed on this primer layer. The primer composition for silicone pressure-sensitive adhesives according to the present invention is useful in particular for producing a laminate in which the silicone pressure-sensitive adhesive is strongly adhered to the surface of a plastic film substrate and in which the durability of the adhesion is also excellent, and can be utilized to produce laminates in a wide range of fields.
[0038] Though there are no particular limitations on the applications of laminates obtained using the primer composition for silicone pressure-sensitive adhesives of the present invention, the representative applications of laminates are exemplified as silicone pressure-sensitive adhesive tapes or sheets. And, such laminates are useful and preferred as heat-resistant pressure-sensitive adhesive tapes, pressure-sensitive adhesive tapes for electrical insulation service, heat-seal pressure-sensitive adhesive tapes, pressure-sensitive adhesive tapes for masking applications, and so forth.
Examples
[0039] The present invention is specifically described by the practical examples and comparative examples given below, but the present invention is not limited to these practical examples. In the practical examples and comparative examples that follow, "parts" denotes "mass parts" and ppm denotes mass-ppm.
[0040] [Primer composition production: Practical Examples 1 to 1 1 and Comparative Examples 1 to 13]
The primer compositions used in the practical examples and comparative
examples were prepared by introducing the following into a mixer and stirring to uniformity at normal temperature:
(Vi polymer): a dimethylpolysiloxane having the vinyl group at both molecular chain terminals, with the structure shown in Tables 1 to 7, 100 parts,
(SiH polymer): a straight-chain methylhydrogenpolysiloxane having trimethylsiloxy terminals or methylhydrogensiloxane/dimethylsiloxane copolymer having trimethylsiloxy terminals, or branched-chain methylhydrogenpolysiloxane with the structure shown in Tables 1 to 7, 2.5 parts,
(Catalyst): a platinum-based catalyst, i.e., a chloroplatinic acid/ 1,3 -diethynyl- 1 ,1 , 3,3- tetramethyldisiloxane complex, 100 ppm as platinum,
0.66 part methylbutynol,
900 parts toluene, and
1 ,000 parts isooctane.
The H/Vi ratio for each primer composition is given in Tables 1 to 7.
[0041] [Fabrication of the silicone pressure-sensitive adhesive tapes for evaluation:
Practical Examples 1 to 8 and Comparative Examples 1 to 8]
(1) A 50 μm-fhick polyethylene terephthalate film (PET) was used as the plastic film substrate.
(2) A mixture of the following was used as the silicone pressure-sensitive adhesive composition: 100 parts of a silicone pressure-sensitive adhesive for hydrosilylation reaction-curing, product name: SD4593PSA, from Dow Corning Toray Co., Ltd.; 0.75 part of an SiH-containing siloxane-based crosslinking agent, product name: BY24-741 , from Dow Corning Toray Co., Ltd.; 100 ppm as platinum of a platinum-based catalyst,
1. e., a chloroplatinic acid/ 1 ,3 -diethynyl- 1 ,1 , 3, 3 -tetramethyldisiloxane complex; and 12.5 parts toluene.
(3) A primer layer was formed on the plastic film substrate by applying the primer composition using a #3 Mayer bar and curing by heating for 1 minute at 130°C. However, coating with a primer composition was not performed in but only in Comparative
Example 8.
(4) The silicone pressure-sensitive adhesive was then coated on the primer layer in a thickness of 30 μm after toluene evaporation and was cured by heating for 3 minutes at 100°C. Cutting to a width of 25 mm then provided a silicone pressure-sensitive adhesive tape bearing a silicone pressure-sensitive adhesive layer.
[0042] [Evaluation of the adhesiveness of the silicone pressure-sensitive adhesive tapes by a tearing method: Practical Examples 1 to 8 and Comparative Examples 1 to 8]
A tearing method was used to evaluate the adhesiveness between the silicone pressure-sensitive adhesive layer and the plastic film tape in the silicone pressure- sensitive adhesive tape. Thus, the adhesiveness was evaluated based on the degree of elongation of the silicone pressure-sensitive adhesive layer when the plastic film tape, i.e., the substrate, was torn. The silicone pressure-sensitive adhesive layer exhibits a short elongation when the adhesiveness to the plastic film tape is excellent.
For the specific evaluation, a 1.5 mm-long cut was introduced in the width direction of the silicone pressure-sensitive adhesive tape obtained by the method
described above. The silicone pressure-sensitive adhesive tape was then torn by gradually applying force to this cut and the silicone pressure-sensitive adhesive layer was stretched in the slit length direction. The distance between the plastic film tapes when the silicone pressure-sensitive adhesive layer was completely severed, i.e., the distance between the corners of the plastic film tapes, was measured and recorded. The distance between the plastic film tapes = the maximum distance that the silicone pressure-sensitive adhesive layer is stretched without undergoing scission, i.e., the maximum elongation.
[0043] Because the silicone pressure-sensitive adhesive layer exhibits elasticity, the silicone pressure-sensitive adhesive layer can be stretched for a long distance by an external force when the adhesiveness between the silicone pressure-sensitive adhesive layer and the plastic film tape is low. However, when the silicone pressure-sensitive adhesive layer strongly adheres to the plastic film tape, rupture ends up occurring at a short distance between the plastic film tape. Thus, the evaluation is carried out on the basis that a greater adhesive strength is indicated by a shorter distance between the plastic film tapes when the silicone pressure-sensitive adhesive is completely severed. Accordingly, the evaluation was carried out on the following scale for gradual tearing from the cut in the slit length direction as described above.
x x : elongation of the silicone pressure-sensitive adhesive layer without scission > 100 mm, particularly severe
x : elongation of the silicone pressure-sensitive adhesive layer without scission =
40 to 100 mm, severe
Δ : elongation = 25 to 40 mm, small
+ : elongation = 10 to 25 mm, minor
+ + : elongation = 0 to 10 mm, either completely absent or very minor
[0044] [Practical Examples 1 to 8 and Comparative Examples 1 to 8: Adhesiveness- improving effect for hydrosilylation reaction-curable silicone pressure-sensitive adhesives]
The results of the adhesiveness evaluations are shown in Tables 1 to 4 for primer compositions according to practical examples of the present invention and comparative examples, for the use of a hydrosilylation reaction-curable silicone pressure-sensitive adhesive as the silicone pressure-sensitive adhesive and the use of a polyethylene terephthalate film tape for the plastic film tape.
[0045] The individual siloxane units are indicated in Tables 1 to 4 using the following abbreviations.
ViM : vinyldimethylsiloxy unit
M Vi · vinyldimethylsiloxy unit
M trimethylsiloxy unit
D dimethylsiloxy unit
DH methylhydrogensiloxy unit
methylsiloxy unit
[0046] As shown in Tables 1 and 2, the primer compositions in Practical Examples 1 to 8 were shown to have a substantial adhesiveness-improving effect, while in particular the primer compositions in Practical Examples 1 to 5, which used a component (B) in which
H
D was at least 100 and DH (D + DH + T) was at least 0.9, were shown to have a very substantial adhesiveness-improving effect.
In addition, Practical Examples 1 to 5, in which H/Vi was at least 10.0, were also shown to have a better adhesiveness-improving effect than Practical Examples 6 to 8, in which H/Vi was at least 8.0 but less than 10.
As shown in Tables 3 and 4, on the other hand, the adhesiveness-improving effect of the primer composition was found to be poor in all of the following: Comparative Examples 1 , 2, 3, and 7, which used an SiH polymer having a short molecular chain length, i.e., a component (B) with a DH of less than 100; Comparative Examples 2, 4, and
5, which used a component (B) with a DH /(D + DH + T) of less than 0.8; and
Comparative Examples 6 and 7, which used a vinyl polymer, i.e., vinyl-terminated dimethylpolysiloxane with a short molecular chain length, i.e., a component (A) having
D328-
It may thus be understood that claims 1, 2, and 3 of the present application are supported by the aforementioned practical examples and comparative examples and are clear and unambiguous.
[0047] With regard to the straight-chain methylhydrogenpolysiloxanes disclosed in the Specification of Patent Reference 3, in all instances goes no further than 45 or DH goes no further than 45 and DH /(D + DH + T) is less than 0.8, and thus these correspond to the comparative examples described above. Accordingly, it can be concluded that the primer compositions of Practical Examples 1 to 8 provide a substantially superior adhesiveness-improving effect over the primer compositions disclosed in Patent
Reference 3.
[0048] [Fabrication of silicone pressure-sensitive adhesive tapes for evaluation and evaluation: Practical Examples 9 to 1 1 and Comparative Examples 9 to 13]
(1') A 25 μm-thick polyimide film (PI) cut to a width of 25 mm was used as the plastic film substrate.
(2') A mixture of the following was used as the silicone pressure-sensitive adhesive composition: 100 parts of a silicone pressure-sensitive adhesive for organoperoxide- curing, product name: 7406VLO ADHESIVE, from Dow Corning Corporation; 0.15 part of a benzoyl peroxide-containing catalyst paste, product name: NYPER BMT-K40, from NOF Corporation, NYPER is a registered trademark of NOF Corporation; and 50 parts toluene.
(3') A primer layer was formed on one side of the plastic film tape by applying the primer composition using a #3 Mayer bar and curing by heating for 1 minute at 130°C. However, coating with a primer composition was not performed in but only in Comparative
Example 8.
(4') The silicone pressure-sensitive adhesive composition was then coated in a thickness of 30 μm after toluene evaporation and was cured by heating for 3 minutes at 70°C and 5 minutes at 180°C. Cutting to a width of 25 mm then provided a silicone pressure- sensitive adhesive tape bearing a silicone pressure-sensitive adhesive layer.
[0049] [Evaluation of the adhesiveness of the silicone pressure-sensitive adhesive tapes by a tearing method: Practical Examples 9 to 1 1 and Comparative Examples 9 to 13]
The adhesiveness between the silicone pressure-sensitive adhesive layer and the polyimide film tape in the silicone pressure-sensitive adhesive tape was evaluated using the same tearing method as used to evaluate the adhesiveness for the hydrosilylation- curable silicone pressure-sensitive adhesive.
[0050] [Practical Examples 9 to 1 1 and Comparative Examples 9 to 13: Adhesiveness- improving effect for organoperoxide-curable silicone pressure-sensitive adhesives]
The results of the adhesiveness evaluations are shown in Tables 5 to 7 for primer compositions according to practical examples of the present invention and comparative examples, for the use of an organoperoxide-curable silicone pressure-sensitive adhesive as the silicone pressure-sensitive adhesive and the use of a polyimide film tape for the plastic film tape. The abbreviations used in these tables are the same abbreviations as used in Tables 1 to 4.
As shown in Tables 5 to 7, the adhesiveness-improving effect of the primer composition was significant in all of Examples 9 to 1 1, while the adhesiveness-improving effect of the primer composition was unsatisfactory in Comparative Examples 9 to 13.
Thus, the primer compositions in Practical Examples 9 to 1 1 , which used a component (B) in which DH was at least 100 and DH /(D + DH + T) was at least 0.9, were shown to have a substantial adhesiveness-improving effect.
On the other hand, the adhesiveness-improving effect of the primer composition was found to be unsatisfactory in all of the following: Comparative Examples 9 and 13, which used an SiH polymer having a short molecular chain length, i.e., a component (B) with a D of less than 100; Comparative Examples 10 and 1 1 , which used a component
(B) with a DH /(D + DH + T) of less than 0.8; and Comparative Examples 12 and 13, which used a vinyl polymer with a short molecular chain length, i.e., a component (A) having D328-
[0051] In Tables 6 and 7, a maximum elongation for the silicone pressure-sensitive adhesive layer of 30 mm occurred in the comparative examples; this occurred because the sheet-form substrate is polyimide film tape, and organoperoxide-curable silicone pressure-sensitive adhesives generally have a better adhesiveness for plastic tapes than hydrosilylation reaction-curable silicone pressure-sensitive adhesives.
It may thus be understood that claims 1 , 2, and 3 of the present application are supported by the aforementioned practical examples and comparative examples and are clear and unambiguous.
[0052] With regard to the straight-chain methylhydrogenpolysiloxanes disclosed in the Specification of Patent Reference 3, in all instances DH goes no further than 45 or D goes no further than 45 and DH/(D + DH + T) is less than 0.8, and thus these correspond to the comparative examples described above. Accordingly, it can be concluded that the primer compositions of Practical Examples 9 to 1 1 provide a substantially superior adhesiveness-improving effect over the primer compositions disclosed in Patent
Reference 3.
[0053] [Table 1]
[0054] [Table 2]
[0055] [Table 31
^r
[0056] [ Table 41
[0057] Table 51
[0058] [Table 6]
Comparative
9 10 1 1 example
SiH polymer MDH 50M MDH 54D25M M3DH 14oD6oT
D 0 25 60
DH 50 54 140
SiH
T 0 0 1 polymer
DH/(D+DH+T) 1.0 0.68 0.70
SiH content
1.556 1.012 1.054 [mole/100 g]
component (A) viMD798Mvi
Vi D 798
polymer Vi content
0.0033
[mole/ 100 g]
H/Vi 1 1.68 7.60 7.92 max. elongation [mm] 30 35 40 evaluation Δ Δ Δ
[0059] [Table 7]
[0060] [Industrial Applicability]
The primer composition of the present invention for use with silicone pressure- sensitive adhesives is useful for bringing about a strong adhesion between the silicone pressure-sensitive adhesive and a sheet-form substrate when the silicone pressure-sensitive adhesive is applied to the sheet-form substrate such as a plastic film substrate.
The laminate of the present invention is useful as a silicone pressure-sensitive adhesive tape, for example, a heat-resistant pressure-sensitive adhesive tape, pressure- sensitive adhesive tape for electrical insulation service, heat-seal pressure-sensitive adhesive tape, pressure-sensitive adhesive tapes for masking applications, and so forth. The silicone pressure-sensitive adhesive tape of the present invention is useful as a heat- resistant pressure-sensitive adhesive tape, pressure-sensitive adhesive tape for electrical insulation service, heat-seal pressure-sensitive adhesive tape, pressure-sensitive adhesive tapes for masking applications, and so forth.
Claims
1. A primer composition for silicone pressure-sensitive adhesives, the primer
composition comprising the following components (A), (B), and (C):
(A) a diorganopolysiloxane having alkenyl groups at both molecular chain terminals and represented by the following average structural formula (1)
R 1 R22 S iO(R2 2 S iO)PSiR2 2R 1 (1) wherein
R1 is a C2- 10 alkenyl group,
2
R is a C1- 10 monovalent hydrocarbyl group or monovalent halogenated hydrocarbyl group that does not contain an aliphatically unsaturated bond, and P + 2 is a number that on average is in the range from 400 to 2,000;
(B) an organohydrogenpolysiloxane represented by the following average compositional formula (2)
(R33 SiO1/2)k(R3 HSiO2/2)m(R32SiO2/2)n(R3 SiO3/2)p (2) wherein
3
R is a Cj_10 monovalent hydrocarbyl group or monovalent halogenated hydrocarbyl group that does not have an aliphatically unsaturated bond,
"k" is a number that on average is (2 + p),
"m" is a number that on average is in the range from 100 to 500,
"n" and "p" are each numbers that on average are greater than or equal to 0, and
"m", "n", and "p" are numbers that on average are in ranges that satisfy the relationships 100≤ m + n + p≤ 500 and 0.8≤ m/(m + n + p)≤ 1 ; and
(C) a hydrosilylation reaction catalyst.
2. The primer composition for silicone pressure-sensitive adhesives according to
claim 1, wherein component (B) is a straight-chain organohydrogenpolysiloxane represented by the following average structural formula (3)
R33 SiO(R3 HSiO2/2)m l (R32 SiO2/2)n l SiR33 (3) wherein R is a C1- 10 monovalent hydrocarbyl group or monovalent halogenated hydrocarbyl group that does not have an aliphatically unsaturated bond,
"ml " is a number that on average is in the range from 100 to 500,
"nl " is a number that on average is greater than or equal to 0, and
ml and nl are numbers that on average are in ranges that satisfy the relationships 100≤ ml + nl≤ 500 and 0.9≤ ml/(ml + nl)≤ 1.
The primer composition for silicone pressure-sensitive adhesives according to claim 1 , wherein P + 2 in average structural formula (1) is a number which on average is in the range from 450 to 1 ,500.
A laminate comprising
a sheet-form substrate,
a primer layer that is provided by the cure on the sheet-form substrate of a primer composition for silicone pressure-sensitive adhesives according to any one of claims 1 to 3, and
a silicone pressure-sensitive adhesive layer formed on the primer layer.
The laminate according to claim 4, wherein the silicone pressure-sensitive adhesives are hydrosilylation reaction-curable silicone pressure-sensitive adhesives.
The laminate according to claim 4, wherein the sheet-form substrate is a plastic film substrate.
A silicone pressure-sensitive adhesive tape comprising the laminate according to claim 4 wherein the sheet-form substrate is a plastic film tape.
A silicone pressure-sensitive adhesive tape comprising the laminate according to claim 7, wherein the plastic film tape is a heat-resistant plastic film tape.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010-294635 | 2010-12-31 | ||
| JP2010294635 | 2010-12-31 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| WO2012091167A2 true WO2012091167A2 (en) | 2012-07-05 |
| WO2012091167A3 WO2012091167A3 (en) | 2015-10-08 |
Family
ID=45688206
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2011/080586 WO2012091167A2 (en) | 2010-12-31 | 2011-12-27 | Primer composition for silicone pressure-sensitive adhesive, laminate and silicone pressure-sensitive adhesive tape |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP2012149240A (en) |
| TW (1) | TW201233753A (en) |
| WO (1) | WO2012091167A2 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016160749A1 (en) * | 2015-03-31 | 2016-10-06 | Rogers Corporation | Substrates, laminates, and assemblies for flexible heaters, flexible heaters, and methods of manufacture |
| US9567501B2 (en) | 2014-02-27 | 2017-02-14 | Shin-Etsu Chemical Co., Ltd. | Silicone pressure-sensitive adhesive composition having improved substrate adhesion and pressure-sensitive adhesive article |
| WO2020248181A1 (en) * | 2019-06-13 | 2020-12-17 | Dow Silicones Corporation | Silicone pressure sensitive adhesive composition and preparation and use thereof in protective films for ultrasonic fingerprint sensors |
| US11390715B2 (en) | 2017-11-07 | 2022-07-19 | Dow Toray Co., Ltd. | Organopolysiloxane composition |
| US11560497B2 (en) | 2015-05-28 | 2023-01-24 | 3M Innovative Properties Company | Adhesive sheet |
| US11655367B2 (en) | 2017-11-07 | 2023-05-23 | Dow Toray Co., Ltd. | Organopolysiloxane composition |
| US11702574B2 (en) | 2018-01-16 | 2023-07-18 | Shin-Etsu Chemical Co., Ltd. | Adhesive silicone composition and an adhesive film or tape |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102320575B1 (en) | 2014-06-18 | 2021-11-02 | 신에쓰 가가꾸 고교 가부시끼가이샤 | Silicone adhesive composition having excellent substrate adhesion, and adhesive product |
| CN110506087B (en) * | 2017-04-12 | 2022-03-01 | 信越化学工业株式会社 | Primer composition for silicone pressure sensitive adhesive and article |
| JP7358174B2 (en) * | 2019-10-08 | 2023-10-10 | 信越化学工業株式会社 | Primer composition for silicone adhesive |
| WO2022202807A1 (en) * | 2021-03-26 | 2022-09-29 | 日東電工株式会社 | Layered body and primer composition |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4591622A (en) | 1984-10-29 | 1986-05-27 | Dow Corning Corporation | Silicone pressure-sensitive adhesive process and product thereof |
| US5300171A (en) | 1991-08-22 | 1994-04-05 | Dow Corning Corporation | Curable silicone pressure sensitive adhesive tape and bonding method employing same |
| JPH0639584B2 (en) | 1989-06-26 | 1994-05-25 | 信越化学工業株式会社 | Adhesive tape |
| JP2002338890A (en) | 2000-03-23 | 2002-11-27 | Shin Etsu Chem Co Ltd | Primer composition for silicone pressure-sensitive adhesive |
| JP2010184953A (en) | 2009-02-10 | 2010-08-26 | Shin-Etsu Chemical Co Ltd | Silicone adhesive tape and method for producing the same |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2875758B2 (en) * | 1994-12-28 | 1999-03-31 | 東芝シリコーン株式会社 | Adhesive sheet |
| DE60119416T2 (en) * | 2000-03-23 | 2007-05-03 | Shin-Etsu Chemical Co., Ltd. | Primer composition for pressure-sensitive adhesives based on silicones |
| JP5060873B2 (en) * | 2007-08-24 | 2012-10-31 | 東レ・ダウコーニング株式会社 | Silicone pressure-sensitive adhesive composition and pressure-sensitive adhesive tape or sheet |
-
2011
- 2011-12-26 JP JP2011282929A patent/JP2012149240A/en active Pending
- 2011-12-27 WO PCT/JP2011/080586 patent/WO2012091167A2/en active Application Filing
- 2011-12-30 TW TW100149833A patent/TW201233753A/en unknown
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4591622A (en) | 1984-10-29 | 1986-05-27 | Dow Corning Corporation | Silicone pressure-sensitive adhesive process and product thereof |
| JPH0639584B2 (en) | 1989-06-26 | 1994-05-25 | 信越化学工業株式会社 | Adhesive tape |
| US5300171A (en) | 1991-08-22 | 1994-04-05 | Dow Corning Corporation | Curable silicone pressure sensitive adhesive tape and bonding method employing same |
| JP2002338890A (en) | 2000-03-23 | 2002-11-27 | Shin Etsu Chem Co Ltd | Primer composition for silicone pressure-sensitive adhesive |
| JP2010184953A (en) | 2009-02-10 | 2010-08-26 | Shin-Etsu Chemical Co Ltd | Silicone adhesive tape and method for producing the same |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9567501B2 (en) | 2014-02-27 | 2017-02-14 | Shin-Etsu Chemical Co., Ltd. | Silicone pressure-sensitive adhesive composition having improved substrate adhesion and pressure-sensitive adhesive article |
| WO2016160749A1 (en) * | 2015-03-31 | 2016-10-06 | Rogers Corporation | Substrates, laminates, and assemblies for flexible heaters, flexible heaters, and methods of manufacture |
| GB2550754A (en) * | 2015-03-31 | 2017-11-29 | Rogers Corp | Substrates, laminates, and assemblies for flexible heaters, flexible heaters, and methods of manufacture |
| US11560497B2 (en) | 2015-05-28 | 2023-01-24 | 3M Innovative Properties Company | Adhesive sheet |
| US11390715B2 (en) | 2017-11-07 | 2022-07-19 | Dow Toray Co., Ltd. | Organopolysiloxane composition |
| US11655367B2 (en) | 2017-11-07 | 2023-05-23 | Dow Toray Co., Ltd. | Organopolysiloxane composition |
| US11702574B2 (en) | 2018-01-16 | 2023-07-18 | Shin-Etsu Chemical Co., Ltd. | Adhesive silicone composition and an adhesive film or tape |
| WO2020248181A1 (en) * | 2019-06-13 | 2020-12-17 | Dow Silicones Corporation | Silicone pressure sensitive adhesive composition and preparation and use thereof in protective films for ultrasonic fingerprint sensors |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2012091167A3 (en) | 2015-10-08 |
| JP2012149240A (en) | 2012-08-09 |
| TW201233753A (en) | 2012-08-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2012091167A2 (en) | Primer composition for silicone pressure-sensitive adhesive, laminate and silicone pressure-sensitive adhesive tape | |
| TWI779061B (en) | Pressure-sensitive adhesive layer-forming organopolysiloxane composition and use thereof | |
| JP5309714B2 (en) | Silicone pressure-sensitive adhesive composition having antistatic properties and silicone pressure-sensitive adhesive tape | |
| JP6481646B2 (en) | Double-sided differential release paper or double-sided differential release film | |
| JP2734809B2 (en) | Silicone adhesive composition | |
| JPH01154740A (en) | Adhesive structure | |
| US11680194B2 (en) | Method for producing silicone-based adhesive | |
| JPWO2020121930A1 (en) | Silicone Adhesive Compositions and Their Applications | |
| JP5115300B2 (en) | Silicone adhesive composition and silicone adhesive tape with good substrate adhesion | |
| JPWO2020121939A1 (en) | Silicone Pressure Sensitive Adhesive Compositions and Their Applications | |
| JP2009154457A (en) | Release film | |
| JP2011012092A (en) | Addition reaction-curable silicone pressure-sensitive adhesive composition, pressure-sensitive adhesive film using the same, and method for producing pressure-sensitive adhesive film | |
| EP3904085A1 (en) | Curable silicone composition, release coating agent comprising said composition, release film obtained using said release coating agent, and layered product including said release film | |
| TW201843237A (en) | Silicone composition for manufacturing release paper or release film | |
| JP2013139509A (en) | Primer composition for silicone pressure-sensitive adhesive, laminate, and silicone pressure-sensitive adhesive tape | |
| CN113453888A (en) | Curable silicone composition, release coating agent formed from the composition, release film using the release coating agent, and laminate comprising the release film | |
| EP3831908A1 (en) | Silicone adhesive agent composition, and adhesive tape or adhesive film using same | |
| JP5190284B2 (en) | Separator manufacturing method, separator, and adhesive tape with separator | |
| EP3904081B1 (en) | Curable silicone composition, release coating agent comprising said composition, release film obtained using said release coating agent, and layered product including said release film | |
| JP2008024777A (en) | Addition curable silicone adhesive composition for silicone rubber and adhesive tape obtained from the composition | |
| JP3719796B2 (en) | Adhesive material | |
| TWI767036B (en) | Silicone pressure-sensitive adhesive composition | |
| JP4900928B2 (en) | Method for removing uncured silicone from protective film | |
| JP3290581B2 (en) | Peelable silicone composition for silicone adhesive | |
| CN114981361A (en) | Curable organopolysiloxane composition, release coating agent formed from the composition, and laminate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| NENP | Non-entry into the national phase in: |
Ref country code: DE |
|
| 122 | Ep: pct app. not ent. europ. phase |
Ref document number: 11854076 Country of ref document: EP Kind code of ref document: A2 |