JP2004202966A - Silicone laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silicone laminate showing good adhesion without a primer treatment and an adhesive on an adhesive surface without adding a special adhesive promotor to a silicone composition to be used and without necessitating a special ascertainment of fabrication conditions. <P>SOLUTION: The laminate is composed of a cured material of an organopolysiloxane composition (I) containing an aliphatic unsaturated group-containing organopolysiloxane (A-1), an aliphatic unsaturated group-containing organic compound (A-2), (A-1) and (A-2) being referred as (A), an organohydrogenpolysiloxane (B) and a hydrosilylation catalyst (C) and a cured material of an organopolysiloxane composition (II) containing an aliphatic unsaturated group-containing organopolysiloxane (D-1), an aliphatic unsaturated group-containing organic compound (D-2), (D-1) and (D-2) being referred as (D), an organohydrogenpolysiloxane (E) and a hydrosilylation catalyst (F) wherein the molar ratio p of the aliphatic unsaturated group in (A) to SiH group of (B) is smaller than the molar ratio q of the aliphatic unsaturated group in (D) to SiH group of (E). <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

【００６１】
【発明の効果】
本発明のシリコーン積層体は、プライマー処理をしなくても、付加硬化型オルガノポリシロキサン組成物の硬化物同士が接着し、一体成型のシリコーン積層体を形成することができる。従って、意匠物用、特にシリコーンゴム製キートップ、衣類・シューズ用などの装飾用マークやロゴに用いられるシリコーン樹脂製下地材に対するマーキングインク材、立体ロゴ材として有用である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a silicone laminate, and more specifically, to a cured product of an addition-curable organopolysiloxane composition and a cured product of an addition-curable organopolysiloxane composition that are well bonded without using a primer treatment or an adhesive. The present invention relates to a silicone laminate with a product.
[0002]
[Prior art]
In recent years, curable silicone compositions have been used as decorative designs (emblems, logos, etc.) not limited to clothing, bags, shoes and their uses, and the surface of the cured silicone has a curable silicone composition. Marking with ink and three-dimensional logos are molded. Such a curable silicone composition has been proposed in, for example, Japanese Patent Publication No. 52-14642 and Japanese Patent Application Laid-Open No. 2001-214101.
[0003]
[Patent Document 1]
Japanese Patent Publication No. 52-14642
[Patent Document 2]
JP 2001-214101 A
[0004]
[Problems to be solved by the invention]
However, these compositions do not yet have sufficient adhesion to the previously cured silicone cured product, and it is necessary to use an organic compound or an organic peroxide called various adhesion promoters to improve the adhesion. However, the addition of these components causes problems such as a decrease in storage stability in an uncured state and an increase in cost. When these organic compounds are not used, vulcanization of the silicone composition to be cured first is stopped halfway, and vulcanization is performed together with the other silicone composition in a semi-vulcanized state. Although it is possible to adopt a method such as integral molding, there is a problem that the work process becomes complicated and complicated, such as determining conditions such as a vulcanization temperature and a vulcanization time.
[0005]
The present invention has been made to solve the above problems, and does not require the use of a primer treatment or an adhesive at the interface to be bonded, and does not require the addition of a special adhesion promoter to the silicone composition used. An object of the present invention is to provide a silicone laminate that adheres well and does not require special determination of processing conditions.
[0006]
[Means for Solving the Problems]
The present inventors have conducted various studies to achieve the above object, and as a result, a cured product of the addition-curable organopolysiloxane composition (I) containing the following (A) to (C) and the following (D) To the cured product of the addition-curable organopolysiloxane composition (II) containing (F) to (F), the silicon-bonded hydrogen in the component (B) relative to the total aliphatic unsaturated groups in the component (A) The molar ratio p of the atom (SiH group) and the molar ratio q of the silicon-bonded hydrogen atom (SiH group) in the component (E) to the total aliphatic unsaturated groups in the component (D) are p <q. By doing so, it adheres well without using a primer treatment or adhesive on the interface to be bonded, and without adding a special adhesion promoter to the composition to be used, and furthermore, special determination of processing conditions etc. Silicone laminate that adheres well without need Found that to obtain, the present invention has been accomplished.
[0007]
Therefore, the present invention
(A) (A-1) an organopolysiloxane containing two or more aliphatic unsaturated groups bonded to a silicon atom in one molecule: 80 to 100 parts by weight
(A-2) An organic compound containing at least one aliphatic unsaturated group capable of hydrosilylation reaction with a hydrogen atom bonded to a silicon atom in one molecule: 0 to 20 parts by weight
Amount such that the sum of the component (A-1) and the component (A-2) becomes 100 parts by weight.
(B) an organohydrogenpolysiloxane containing two or more hydrogen atoms bonded to a silicon atom in one molecule: the total number of moles of the aliphatically unsaturated groups in the components (A-1) and (A-2) ( When p represents the ratio (b) / (a) of the number of moles (b) of the hydrogen atom bonded to the silicon atom contained in the component to the component a), an amount satisfying 0.5 ≦ p ≦ 1.5.
(C) Hydrosilylation reaction catalyst: effective amount
A cured product of an organopolysiloxane composition (I) containing
(D) (D-1) an organopolysiloxane containing two or more aliphatic unsaturated groups bonded to a silicon atom in one molecule: 80 to 100 parts by weight
(D-2) An organic compound containing one or more aliphatic unsaturated groups capable of hydrosilylation reaction with a hydrogen atom bonded to a silicon atom in one molecule: 0 to 20 parts by weight
Amount such that the sum of the component (D-1) + the component (D-2) becomes 100 parts by weight.
(E) an organohydrogenpolysiloxane containing two or more hydrogen atoms bonded to a silicon atom in one molecule: the total number of moles of the aliphatically unsaturated groups in the components (D-1) and (D-2) ( Assuming that the ratio (e) / (d) of the number of moles (e) of hydrogen atoms bonded to silicon atoms contained in this component to d) is q, 0.5 <q ≦ 20
(F) Hydrosilylation reaction catalyst: effective amount
Which is a laminate with a cured product of the organopolysiloxane composition (II), wherein the molar ratio p, q satisfies p <q.
[0008]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described in more detail.
The organopolysiloxane composition (I) constituting one layer of the silicone laminate of the present invention comprises:
(A) (A-1) an organopolysiloxane containing two or more aliphatic unsaturated groups bonded to a silicon atom in one molecule: 80 to 100 parts by weight
(A-2) An organic compound containing at least one aliphatic unsaturated group capable of hydrosilylation reaction with a hydrogen atom bonded to a silicon atom in one molecule: 0 to 20 parts by weight
Amount such that the sum of the component (A-1) and the component (A-2) becomes 100 parts by weight.
(B) an organohydrogenpolysiloxane containing two or more hydrogen atoms bonded to a silicon atom in one molecule: the total number of moles of the aliphatically unsaturated groups in the components (A-1) and (A-2) ( Assuming that the ratio (b) / (a) of the number of moles (b) of hydrogen atoms bonded to silicon atoms (ie, SiH groups) contained in this component with respect to a) is (p), 0.5 ≦ p ≦ 1 .5 amount
(C) Hydrosilylation reaction catalyst: effective amount
It contains.
[0009]
[(A) component]
[(A-1) component]
The organopolysiloxane of the component (A-1) is a main component of the composition and contains two or more aliphatic unsaturated groups in one molecule. Examples of the aliphatic unsaturated group include, for example, an alkenyl group having 2 to 8 carbon atoms, preferably about 2 to 4 carbon atoms, such as a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, and a heptenyl group. And particularly preferably a vinyl group. The aliphatic unsaturated group bonded to the silicon atom in the component (A) may be, for example, a molecular chain terminal group (an alkenyl group-containing triorganosiloxy group such as a diorganoalkenylsiloxy group, an organodialkenylsiloxy group, and a trialkenylsiloxy group). And / or molecular side groups (in the form of alkenyl group-containing diorganoloxane units such as organoalkenylsiloxane units and dialkenylsiloxane units).
[0010]
Examples of the organic group bonded to a silicon atom other than an aliphatic unsaturated group such as an alkenyl group in the component (A-1) include, for example, an alkyl group, particularly a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, An alkyl group having 1 to 10 carbon atoms such as a hexyl group, a cyclohexyl group, and a heptyl group; an aryl group, particularly an aryl group having 6 to 14 carbon atoms such as a phenyl group, a tolyl group, a xylyl group, and a naphthyl group; An aralkyl group having 7 to 14 carbon atoms such as a benzyl group and a phenethyl group; and an alkyl halide group, particularly an aralkyl group having 1 carbon atom such as a chloromethyl group, a 3-chloropropyl group and a 3,3,3-trifluoropropyl group. Unsubstituted or halogen-substituted monovalent hydrocarbon groups, such as halogenated alkyl groups (1) to (3), and a methyl group and a phenyl group are particularly preferable.
[0011]
The molecular structure of the component (A-1) includes, for example, a linear structure, a partially branched linear structure, a cyclic structure, a branched structure, and the like. It is preferable to use a linear diorganopolysiloxane in which the chain basically consists of repeating diorganosiloxane units, and both ends of the molecular chain are blocked with a triorganosiloxy group.
[0012]
The viscosity at 23 ° C. of the component (A-1) is in the range of 100 to 500,000 mPa · s because the physical properties of the obtained silicone rubber are good and the workability of the composition is good. It is preferably within the range of 300 to 100,000 mPa · s, and more preferably within the range of 1,000 to 50,000 mPa · s. The degree of polymerization of the component (A-1) (or the number of silicon atoms in the molecule) is preferably about 50 to 5,000, more preferably about 100 to 2,000, and particularly preferably about 200 to 1,200. .
[0013]
Examples of the organopolysiloxane of the component (A-1) include, for example, a dimethylsiloxane / methylvinylsiloxane copolymer having trimethylsiloxy groups at both ends of molecular chains, a methylvinylpolysiloxane having trimethylsiloxy groups at both ends of molecular chains, Trimethylsiloxy group-blocked dimethylsiloxane / methylvinylsiloxane / diphenylsiloxane copolymer at both ends of the chain, dimethylpolysiloxane blocked at both ends of the molecular chain, methylvinylpolysiloxane blocked at both ends of the molecular chain, methylvinylpolysiloxane Dimethylvinylsiloxy-terminal-blocked dimethylsiloxane / methylvinylsiloxane copolymer, dimethylvinylsiloxy-terminal-blocked dimethylsiloxane / methylvinylsiloxane / diphenylsiloxane copolymer at both molecular chains, Child-terminated divinyl trimethylsiloxy group-blocked dimethylpolysiloxane with both molecular chain terminals by trimethylsiloxy blocked with dimethylvinylsiloxy groups, wherein: R¹ _ThreeSiO_0.5(R¹Is as described later) and a siloxane unit represented by the formula: R¹ _TwoR^TwoSiO_0.5(R^TwoIs as described later) and a siloxane unit represented by the formula: R¹ _TwoSiloxane unit represented by SiO and a small amount of formula: SiO_TwoAn organopolysiloxane copolymer comprising a siloxane unit represented by the formula: R¹ _ThreeSiO_0.5And a siloxane unit represented by the formula: R¹ _TwoR^TwoSiO_0.5And a siloxane unit represented by the formula: SiO_TwoAn organopolysiloxane copolymer comprising a siloxane unit represented by the formula: R¹ _TwoR^TwoSiO_0.5And a siloxane unit represented by the formula: R¹ _TwoSiloxane unit represented by SiO and a small amount of formula: SiO_TwoAn organopolysiloxane copolymer comprising a siloxane unit represented by the formula: R¹R^TwoA siloxane unit represented by SiO and a small amount of the formula: R¹SiO_1.5Or a siloxane unit represented by the formula: R^TwoSiO_1.5And an organopolysiloxane copolymer comprising a siloxane unit represented by These can be used alone or in combination of two or more.
[0014]
R in the above formula¹Is an unsubstituted or substituted monovalent hydrocarbon group other than an alkenyl group, for example, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group; a phenyl group, a tolyl group Aryl groups such as benzyl, xylyl and naphthyl groups; aralkyl groups such as benzyl group and phenethyl group; and alkyl halide groups such as chloromethyl group, 3-chloropropyl group and 3,3,3-trifluoropropyl group. Can be In addition, R in the above formula^TwoIs an alkenyl group, for example, a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group and the like.
[0015]
[(A-2) component]
(A-2) A hydrogen atom bonded to a silicon atom (SiH group) in an organic compound containing one or more aliphatic unsaturated groups capable of hydrosilylation reaction with a hydrogen atom bonded to a silicon atom as a component in one molecule. Examples of the aliphatic unsaturated group capable of undergoing a hydrosilylation reaction include an alkenyl group such as a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, a pentenyl group, a hexenyl group, a heptenyl group, and an acryloxy group. Examples of the component (A-2) include alkenyl group-containing aromatic compounds such as α-methylstyrene and diallyl phthalate, and alkenyl group-containing ethers such as vinyl ethyl ether and allyl glycidyl ether. Compounds, alkenyl group-containing heterocyclic compounds such as triallyl isocyanurate, ( (T) one or more aliphatic unsaturated group-containing hydrocarbon compounds containing no silicon atom in the molecule, such as acrylic acid and derivatives thereof such as esters and acid anhydrides, and one or more aliphatic unsaturated groups in the molecule; Having a viscosity at 23 ° C. of preferably less than 100 mPa · s, usually 0.01 to 50 mPa · s, more preferably 0.01 to 30 mPa · s, and still more preferably about 0.1 to 10 mPa · s. Organic silicon compounds such as (poly) siloxane (siloxane oligomer) can be mentioned. The degree of polymerization of the organo (poly) siloxane (siloxane oligomer) or the number of silicon atoms in the molecule is usually 2 to 20, preferably 2 to 10, and more preferably about 2 to 8. As this organosilicon compound, specifically, it has one or more alkenyl groups such as trimethylvinylsilane, trimethoxyvinylsilane, methoxydimethylvinylsilane, divinyldimethylsilane, allyltrimethylsilane, dimethyldivinylsilane, methyltrivinylsilane, and diallyldimethylsilane. Organoalkenyl silane, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,4-bis (dimethylvinylsiloxy) benzene, 1,3,5,7-tetramethyl-1,3 And organo (poly) siloxane (or siloxane oligomer) having one or more alkenyl groups such as 1,5,7-tetravinylcyclotetrasiloxane.
[0016]
The mixing ratio of the components (A-1) and (A-2) is 80 parts by weight: 20 parts by weight to 100 parts by weight: 0 parts by weight, preferably 90 parts by weight: 10 parts by weight to 100 parts by weight. : 0 parts by weight, more preferably 95 parts by weight: 5 parts by weight to 100 parts by weight: 0 parts by weight. This is because if the amount of the component (A-1) is less than 80 parts by weight, the environmental resistance and rubber strength required as a cured silicone product cannot be maintained.
[0017]
[Component (B)]
The organohydrogenpolysiloxane of the component (B) reacts with the components (A-1) and (A-2) and acts as a crosslinking agent. The molecular structure of the organohydrogenpolysiloxane is not particularly limited, and is conventionally produced. For example, various types such as linear, cyclic, branched, and three-dimensional network structures (resin-like) can be used, but are bonded to two or more, preferably three or more silicon atoms in one molecule. It is necessary to have a hydrogen atom (hydrosilyl group represented by SiH), and it is usually desirable to have about 3 to 500, preferably 3 to 200, and more preferably about 3 to 100 SiH groups. As the organohydrogenpolysiloxane, those represented by the following average composition formula (1) are used.
[0018]
R^Three _mH_nSiO_{(4-mn) / 2}          (1)
In the above formula (1), R^ThreeIs an unsubstituted or substituted monovalent hydrocarbon group, usually excluding an aliphatic unsaturated bond, bonded to a silicon atom having 1 to 14 carbon atoms, preferably 1 to 10 carbon atoms.^ThreeExamples of the unsubstituted or substituted monovalent hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, and a cyclohexyl group. Alkyl groups such as octyl group, nonyl group and decyl group; aryl groups such as phenyl group, tolyl group, xylyl group and naphthyl group; aralkyl groups such as benzyl group, phenylethyl group and phenylpropyl group; Substituted or partially substituted by a halogen atom such as fluorine, bromine or chlorine, for example, chloromethyl group, 3-chloropropyl group, bromoethyl group, 3,3,3-trifluoropropyl group, etc. No. R^ThreeThe unsubstituted or substituted monovalent hydrocarbon group is preferably an alkyl group or an aryl group, more preferably a methyl group or a phenyl group. Further, m is a positive number satisfying 0.7 to 2.1, n is 0.001 to 1.0, and m + n satisfies 0.8 to 3.0, and preferably, m is 1.0 to 1.0. 2.0 and n are positive numbers satisfying 0.01 to 1.0 and m + n satisfying 1.5 to 2.5.
[0019]
Two or more, preferably three or more, SiH groups contained in one molecule may be located at the terminal of the molecular chain, at the middle of the molecular chain, or at both. The molecular structure of the organohydrogenpolysiloxane may be any of linear, cyclic, branched, and three-dimensional network structures, but the number of silicon atoms in one molecule (or the degree of polymerization) is as follows. The viscosity is usually about 2 to 1,000, preferably about 3 to 300, more preferably about 4 to 150, and the viscosity at 25 ° C. is usually 0.1 to 5,000 mPa · s, preferably 0.5 to 1 A liquid at room temperature (25 ° C.) of about 2,000 mPa · s, more preferably about 5 to 500 mPa · s is used.
[0020]
The component (B) can be obtained by a known production method. General production methods include, for example, 1,3,5,7-tetramethyl-1,3,5,7-tetrahydrocyclotetrasiloxane (in some cases, the cyclotetrasiloxane and octamethylcyclotetrasiloxane And a siloxane compound as a terminal group source such as hexamethyldisiloxane and 1,3-dihydro-1,1,3,3-tetramethyldisiloxane, or octamethylcyclotetrasiloxane and 1,3 -Easily by equilibrating dihydro-1,1,3,3-tetramethyldisiloxane with a catalyst such as sulfuric acid, trifluoromethanesulfonic acid or methanesulfonic acid at a temperature of about -10 to + 40 ° C. Can be obtained.
[0021]
Examples of the organohydrogenpolysiloxane of the component (B) include a methylhydrogenpolysiloxane having a trimethylsiloxy group at both ends of a molecular chain, a dimethylsiloxane / methylhydrogensiloxane copolymer having a trimethylsiloxy group at both ends thereof, Trimethylsiloxy group-blocked dimethyl siloxane / methyl hydrogen siloxane / methyl phenyl siloxane copolymer at both ends of chain, dimethyl polysiloxane blocked at both ends of molecular chain, dimethyl polysiloxane blocked at both ends of molecular chain Methyl hydrogen siloxane copolymer, molecular chain terminal dimethyl hydrogen siloxy group-blocked dimethyl siloxane / methyl phenyl siloxane copolymer, molecular chain terminal dimethyl amine Mud siloxy groups at methylphenyl polysiloxane, wherein: R^Three _ThreeSiO_0.5And a siloxane unit represented by the formula: R^Three _TwoHSiO_0.5And a small amount of the formula: SiO_TwoAn organopolysiloxane copolymer comprising a siloxane unit represented by the formula: R^Three _TwoHSiO_0.5And a small amount of the formula: SiO_TwoAn organopolysiloxane copolymer comprising a siloxane unit represented by the formula: R^ThreeA siloxane unit represented by HSiO and a small amount of the formula: R^ThreeSiO_1.5Or a siloxane unit represented by the formula: HSiO_1.5And an organopolysiloxane copolymer comprising a siloxane unit represented by These can be used alone or in combination of two or more.
[0022]
R in the above formula^ThreeIs a monovalent hydrocarbon group other than an alkenyl group, and examples thereof include the same groups as defined for the component (A).
[0023]
The blending amount of the component (B) is the total number of moles of the aliphatic unsaturated group bonded to the silicon atom in the component (A-1) and the hydrosilylation-reactive aliphatic unsaturated group in the component (A-2). The ratio p [(b) / (a)] of the number of moles (b) of hydrogen atoms (SiH groups) bonded to silicon atoms in the component (B) to the component (a) is preferably 0.5 to 1.5. Is an amount in the range of 0.7 to 1.1, more preferably 0.8 to 1.0. If the blending amount of the component (B) or the value of p is too small, the composition may not be cured sufficiently. Conversely, if it is too large, the adhesiveness between cured products of the obtained composition may be extremely poor. .
[0024]
[(C) component]
As the catalyst for the hydrosilylation reaction of the component (C), any catalyst can be used as long as it promotes the addition reaction between the aliphatic unsaturated group in the component (A) and the SiH group in the component (B). You may.
[0025]
For example, platinum-based catalysts such as chloroplatinic acid, alcohol-modified chloroplatinic acid, coordination compounds of chloroplatinic acid with olefins, vinylsiloxane or acetylene compounds, palladium-based catalysts such as tetrakis (triphenylphosphine) palladium, chlorotris ( A rhodium-based catalyst such as triphenylphosphine) rhodium is used, and a platinum-based compound is particularly preferred.
[0026]
The amount of the component (C) used is not particularly limited as long as it is an effective amount, but is usually 0.1 to 1 as a weight of the catalytic metal element with respect to the total amount of the components (A) and (B). 2,000 ppm, preferably in a proportion of 1 to 500 ppm, more preferably in a range of 10 to 100 ppm. If the amount is too small, the addition reaction may be remarkably slowed or may not be cured, while if it is too large, cost may be disadvantageous.
[0027]
Next, the organopolysiloxane composition (II) constituting the other layer is:
(D) (D-1) an organopolysiloxane containing two or more aliphatic unsaturated groups bonded to a silicon atom in one molecule: 80 to 100 parts by weight
(D-2) An organic compound containing one or more aliphatic unsaturated groups capable of hydrosilylation reaction with a hydrogen atom bonded to a silicon atom in one molecule: 0 to 20 parts by weight
Amount such that the sum of the component (D-1) + the component (D-2) becomes 100 parts by weight.
(E) an organohydrogenpolysiloxane containing two or more hydrogen atoms bonded to a silicon atom in one molecule: the total number of moles of the aliphatically unsaturated groups in the components (D-1) and (D-2) ( 0.5 <q ≦ 20, where q is the ratio (e) / (d) of the number of moles (e) of hydrogen atoms (SiH groups) bonded to silicon atoms contained in this component to d). amount
(F) Hydrosilylation reaction catalyst: effective amount
It contains.
[0028]
[(D) component]
[(D-1) component]
As the organopolysiloxane of the component (D-1), those similar to the component (A-1) can be exemplified. In this case, the component (D-1) and the component (A-1) may be the same or different.
[0029]
[(D-2) component]
As the organopolysiloxane of the component (D-2), those similar to the component (A-2) can be exemplified. Also in this case, the component (D-2) and the component (A-2) may be the same or different.
[0030]
The mixing ratio of the components (D-1) and (D-2) is 80 parts by weight: 20 parts by weight to 100 parts by weight: 0 parts by weight, preferably 90 parts by weight: 10 parts by weight to 100 parts by weight. : 0 parts by weight, more preferably 95 parts by weight: 5 parts by weight to 100 parts by weight: 0 parts by weight. This is because, if the amount of the component (D-1) is less than 80 parts by weight, environmental resistance and rubber strength required as a cured silicone product cannot be maintained.
[0031]
[(E) component]
As the organohydrogenpolysiloxane of the component (E), those similar to the component (B) are exemplified, but it is preferable to include an organohydrogenpolysiloxane having a structure incompatible with the component (D-1). . Here, the organohydrogenpolysiloxane having an incompatible structure includes, as a monovalent substituent bonded to a silicon atom, a 3,3,3-trifluoropropyl group, a phenyl group, and γ- (meth) acryloxy. Examples thereof include a triorganosiloxy group having a propyl group, a γ-glycidoxypropyl group, and the like, and an organohydrogenpolysiloxane having a diorganosiloxane unit and the like in the molecule.
[0032]
In this case, the ratio of the organohydrogenpolysiloxane (i) having a structure compatible with the component (D-1) to the organohydrogenpolysiloxane (ii) having a structure incompatible with the component is as follows: The molar ratio [(i) / (ii)] of the bonded hydrogen atoms (SiH groups) is preferably from 10: 0 to 0:10, and more preferably from 9: 1 to 2: 8. If the amount of the organohydrogenpolysiloxane having a structure incompatible with the component (D-1) is too large, it may be separated from the siloxane matrix during storage.
[0033]
The amount of the component (E) is based on the total number of moles of the aliphatic unsaturated group bonded to the silicon atom in the component (D-1) and the hydrosilylation-reactive aliphatic unsaturated group in the component (D-2). When the ratio of the number of moles (e) of hydrogen atoms (SiH groups) bonded to silicon atoms in the organohydrogenpolysiloxane to (d) is q [(e) / (d)], 0.5 <q ≦ 20, preferably 0.6 ≦ q ≦ 10, more preferably 0.8 ≦ q ≦ 5. If the amount of the component (E) or the value of q is too small, crosslinking may be insufficient and sufficient rubber strength may not be obtained, or the adhesion between cured products of the composition may be extremely poor. If it is too large, it may be disadvantageous in terms of cost.
[0034]
In the silicone laminate of the present invention, the total aliphatic unsaturated groups in the component (A) relative to the silicon-bonded hydrogen atoms (SiH groups) in the component (B) in the organopolysiloxane composition (I) described above. And the molar ratio q of the total aliphatic unsaturated groups in the component (D) to the silicon-bonded hydrogen atoms (SiH groups) in the component (E) in the organopolysiloxane composition (II), p <q, preferably q / p ≧ 1.2, whereby the cured product of the organopolysiloxane composition (I) and the cured product of the organopolysiloxane composition (II) are Good adhesion at the interface. In this case, it is more preferable that q / p ≧ 1.5, especially q / p ≧ 2. Although the upper limit of q / p is not particularly limited, it is usually q / p ≦ 40, particularly q / p ≦ 10.
[0035]
As the catalyst for the hydrosilylation reaction of the component (F), those similar to the component (C) can be exemplified. Also in this case, the component (F) and the component (C) may be the same or different.
[0036]
The amount of the component (F) is not particularly limited as long as it is an effective amount, but is usually 0.1 to 1 as the weight of the catalytic metal element with respect to the total amount of the components (D) and (E). 2,000 ppm, preferably in a proportion of 1 to 500 ppm, more preferably in a range of 10 to 100 ppm. If the amount is too small, the addition reaction may be remarkably slowed or may not be cured, while if it is too large, cost may be disadvantageous.
[0037]
Further, in the organopolysiloxane compositions (I) and (II) of the present invention, a coloring agent can be used from the viewpoint of design properties. ) Or 100 to 100 parts by weight of the organopolysiloxane composition (II), from 0 to 50 parts by weight, particularly 0.1 to 5 parts by weight is preferable in terms of physical properties.
[0038]
Examples of such coloring agents include inorganic pigments such as ultramarine, iron oxide, titanium oxide, titanium yellow, carbon black, zinc white, and chrome green; anthraquinone violet, anthraquinone blue, induslen blue, alizanin green, and perison red. Organic pigments, metal powder pigments such as aluminum powder, copper powder, bronze powder, tin powder, and the like, phosphorescent pigments, fluorescent pigments, and dyes that do not inhibit curing can be cited, and are appropriately selected in consideration of color tone, saturation, and the like. Is done.
[0039]
[Other ingredients]
In the organopolysiloxane compositions (I) and (II) of the present invention, as the optional components other than the above-mentioned components, all conventionally known control agent compounds which are compounds having a curing inhibitory effect on an addition reaction catalyst are used. Can be used. Examples of such compounds include phosphorus-containing compounds such as triphenylphosphine, nitrogen-containing compounds such as tributylamine, tetramethylethylenediamine, and benzotriazole, sulfur-containing compounds, acetylene-based compounds such as 1-ethynyl-1-hexanol, triallyl. Examples include compounds containing two or more alkenyl groups such as isocyanurates, hydroperoxy compounds, and maleic acid derivatives. The degree of the cure retarding effect of the control agent compound varies greatly depending on the chemical structure of the control agent compound. Therefore, the amount of the control agent compound to be added should be adjusted to an optimum amount for each of the control agent compounds to be used. However, in general, if the amount is too small, long-term storage stability at room temperature cannot be obtained. On the contrary, if the amount is too large, the curing is rather inhibited.
[0040]
As other optional components, for example, fumed silica, crystalline silica, precipitated silica, hollow filler, silsesquioxane, fumed titanium dioxide, magnesium oxide, zinc oxide, iron oxide, aluminum hydroxide, magnesium carbonate, Inorganic fillers such as calcium carbonate, zinc carbonate, layered mica, carbon black, diatomaceous earth, and glass fiber, and these fillers are used as organic compounds such as organoalkoxysilane compounds, organochlorosilane compounds, organosilazane compounds, and low-molecular-weight siloxane compounds. A filler surface-treated with a silicon compound may be used. Examples of the filler include silicone rubber powder and silicone resin powder.
[0041]
The organopolysiloxane compositions (I) and (II) may further contain, as an optional component, an organopolysiloxane containing no silicon-bonded hydrogen atom and no alkenyl group within a range not to impair the object of the present invention. It is optional to add a siloxane, an organic solvent, a creep hardening inhibitor, a heat resistance imparting agent, a flame retardant imparting agent, a plasticizer, a thixotropy imparting agent, a pigment, a dye, a fungicide, and the like.
[0042]
The organopolysiloxane compositions (I) and (II) of the present invention can be produced by mixing the above components by a known method, respectively. It can be used after being diluted with an organic solvent such as toluene, xylene, benzene, or cyclic siloxane.
[0043]
Examples of the method for producing a laminate using the organopolysiloxane compositions (I) and (II) include injection molding, molding and screen molding, and the compositions (I) and (II). ) May be cured first, followed by curing the other to form a laminate, and there is no priority of the composition to the curing order. Further, these compositions may be simultaneously cured to form a laminate. The laminate may be composed of two or more layers as long as they are alternately laminated in the order of the compositions (I) and (II).
[0044]
Here, the curing conditions of the organopolysiloxane compositions (I) and (II) are not particularly limited, and the curing can be performed under known conditions as the curing conditions of the addition reaction-curable organopolysiloxane composition. Preferably, the composition can be cured at 80 to 160 ° C., preferably 120 to 150 ° C., for 0.1 to 4 hours, particularly about 1 to 2 hours.
[0045]
In the silicone laminate of the present invention, cured products of the addition-curable organopolysiloxane composition are adhered to each other without performing a primer treatment, and an integrally molded silicone laminate can be formed. Accordingly, it is useful as a marking ink material and a three-dimensional logo material for a silicone resin base material used for decorative objects such as key tops made of silicone rubber, especially for decoration marks and logos for clothes and shoes.
[0046]
【Example】
Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. In the following examples, Me represents a methyl group, Ph represents a phenyl group, and Vi represents a vinyl group.
[0047]
[Example 1]
84 parts by weight of dimethylpolysiloxane (degree of polymerization: about 510) having a viscosity at 23 ° C. of 10,000 mPa · s and a Vi group content of 0.14% by weight, in which both ends of the molecular chain are blocked with vinyldimethylsiloxy groups. The specific surface area of the silica surface silanol groups blocked by trimethylsilyl groups by surface treatment is 130 m.^Two/ G of hydrophobic silica was charged into a kneader, 5 parts by weight of hexamethylene disilazane and 1.5 parts by weight of water were added with good stirring, and mixed without heating until uniform. The temperature was raised to 170 ° C., followed by mixing for 4 hours, and then the temperature was lowered to room temperature. A base obtained by adding 39.5 parts by weight of the above-mentioned dimethylpolysiloxane having a Vi group content of 0.14% by weight in which both ends of a molecular chain are blocked with vinyldimethylsiloxy groups to 60 parts by weight of the mixture thus obtained. 99.5 parts by weight, 0.5 parts by weight of triallyl isocyanurate, and a complex of chloroplatinic acid and divinyltetramethyldisiloxane having a molecular weight of 23 ° C. 0.2 parts by weight as a platinum catalyst solution (Vi group content 0.4% by weight, platinum atom content 1% by weight) diluted with 600 mPa · s dimethylpolysiloxane, 1,3,5,7- 0.3 parts by weight of tetramethyl-1,3,5,7-tetravinyltetrasiloxane was added and mixed uniformly to prepare a preparation liquid. Next, 1.3 parts by weight of methyl hydrogen polysiloxane having the following average molecular formula and 0.5 parts by weight of bengalara so that the adhesion state can be visually checked are added to the mixture, and the mixture is uniformly mixed. The product (I) was prepared.
Me_TwoHSiO (MeHSiO)_5.7(Me_TwoSiO)_12.3SiHMe_Two
The molar ratio (SiH / SiVi) of silicon-bonded hydrogen atoms to silicon-bonded vinyl groups in the composition (I) was about 0.7.
[0048]
Next, 1.9 parts by weight of hydrogenpolysiloxane having the following average molecular weight and 0.5 parts by weight of titanium oxide were added to the above-prepared solution so that the adhesion state could be visually confirmed, and the mixture was uniformly mixed. Compound (II) was prepared.
Me_ThreeSiO (MeHSiO)₂₀(Me_TwoSiO)₁₈SiMe_Three
The molar ratio (SiH / SiVi) of silicon-bonded hydrogen atoms to silicon-bonded vinyl groups in this composition (II) was about 1.5.
[0049]
The composition (I) was poured into a metal frame for press having a depth of about 2 mm, and heated at 150 ° C. for 10 minutes to produce a cured sheet. Next, the sheet was allowed to cool to room temperature, transferred to a metal frame for press having a depth of about 4 mm, and the composition (II) was poured therein, and a laminate was prepared by heat curing at 150 ° C./10 minutes. However, a portion to which a measuring jig (chuck) to be used later for measuring the adhesive strength was protected with a Teflon liner so that it could be separated into two layers.
Next, the laminate was cut into strips, and the peel adhesive strength was measured by a method according to JIS K-6256. Table 1 shows the measurement results of the peel adhesive strength.
[0050]
[Example 2]
Composition (I) was prepared in the same manner as in Example 1 except that the amount of methyl hydrogen polysiloxane having the following average molecular formula was changed to 0.6 parts by weight and triallyl isocyanurate was not added. .
Me_TwoHSiO (MeHSiO)_5.7(Me_TwoSiO)_12.3SiHMe_Two
The molar ratio (SiH / SiVi) of silicon-bonded hydrogen atoms to silicon-bonded vinyl groups in the composition (I) was about 0.7.
[0051]
A composition (II) was prepared in the same manner as in Example 1 except that the amount of methyl hydrogen polysiloxane having the following average molecular formula was changed to 0.9 parts by weight, and triallyl isocyanurate was not added. did.
Me_ThreeSiO (MeHSiO)₂₀(Me_TwoSiO)₁₈SiMe_Three
The molar ratio (SiH / SiVi) of silicon-bonded hydrogen atoms to silicon-bonded vinyl groups in this composition (II) was about 1.5. Table 1 shows the measurement results of the peel adhesive strength.
[0052]
[Example 3]
Composition (I) was prepared in the same manner as in Example 2 except that methyl hydrogen polysiloxane was changed to 1.0 part by weight of methyl hydrogen polysiloxane having the following average molecular formula.
Me_TwoHSiO (MeHSiO)_5.7(Me_TwoSiO)_12.3SiHMe_Two
The molar ratio (SiH / SiVi) of silicon-bonded hydrogen atoms to silicon-bonded vinyl groups in the composition (I) was about 1.3.
[0053]
A composition (II) was prepared in the same manner as in Example 2, except that methyl hydrogen polysiloxane was changed to 1.7 parts by weight of methyl hydrogen polysiloxane having the following average molecular formula.
Me_ThreeSiO (MeHSiO)₈SiMe_Three
The molar ratio (SiH / SiVi) of silicon-bonded hydrogen atoms to silicon-bonded vinyl groups in this composition (II) was about 5.0. Table 1 shows the measurement results of the peel adhesive strength.
[0054]
[Example 4]
Composition (I) was prepared in the same manner as in Example 2 except that methyl hydrogen polysiloxane was changed to 0.6 part by weight of methyl hydrogen polysiloxane having the following average molecular formula.
Me_ThreeSiO (MeHSiO)₂₀(Me_TwoSiO)₁₈SiMe_Three
The molar ratio (SiH / SiVi) of the hydrogen atom bonded to the silicon atom to the vinyl group bonded to the silicon atom in the composition (I) was about 1.0.
[0055]
A composition (II) was prepared in the same manner as in Example 2 except that the methyl hydrogen polysiloxane was changed to 0.6 parts by weight of an organo hydrogen polysiloxane having a phenyl group and a methyl group having the following average molecular formula. .
Me_ThreeSiO (MeHSiO)₈(Ph_TwoSiO) (Me_TwoSiO) SiMe_Three
The molar ratio (SiH / SiVi) of silicon-bonded hydrogen atoms to silicon-bonded vinyl groups in the composition (II) was about 1.2. Table 1 shows the measurement results of the peel adhesive strength.
[0056]
[Comparative Example 1]
Composition (I) was prepared in the same manner as in Example 2 except that the addition amount of methyl hydrogen polysiloxane having the following average molecular formula was changed to 0.78 parts by weight.
Me_TwoHSiO (MeHSiO)_5.7(Me_TwoSiO)_12.3SiHMe_Two
The molar ratio (SiH / SiVi) of the hydrogen atom bonded to the silicon atom to the vinyl group bonded to the silicon atom in the composition (I) was about 1.0.
[0057]
A composition (II) was prepared in the same manner as in Example 2, except that the amount of methyl hydrogen polysiloxane having the following average molecular formula was changed to 0.58 parts by weight.
Me_ThreeSiO (MeHSiO)₂₀(Me_TwoSiO)₁₈SiMe_Three
The molar ratio (SiH / SiVi) of silicon-bonded hydrogen atoms to silicon-bonded vinyl groups in the composition (II) was about 1.0. Table 1 shows the measurement results of the peel adhesive strength.
[0058]
[Comparative Example 2]
Composition (I) was prepared in the same manner as in Example 2 except that methyl hydrogen polysiloxane was changed to 0.58 parts by weight of methyl hydrogen polysiloxane having the following average molecular formula.
Me_ThreeSiO (MeHSiO)₂₀(Me_TwoSiO)₁₈SiMe_Three
The molar ratio (SiH / SiVi) of the hydrogen atom bonded to the silicon atom to the vinyl group bonded to the silicon atom in the composition (I) was about 1.0.
[0059]
A composition (II) was prepared in the same manner as in Example 2 except that the methyl hydrogen polysiloxane was changed to 0.58 parts by weight of an organo hydrogen polysiloxane having a phenyl group and a methyl group having the following average molecular formula. .
Me_ThreeSiO (MeHSiO)₈(Ph_TwoSiO)_TwoSiMe_Three
The molar ratio (SiH / SiVi) of silicon-bonded hydrogen atoms to silicon-bonded vinyl groups in the composition (II) was about 1.0. Table 1 shows the measurement results of the peel adhesive strength.
[0060]
[Table 1]

[0061]
【The invention's effect】
In the silicone laminate of the present invention, cured products of the addition-curable organopolysiloxane composition are adhered to each other without performing a primer treatment, and an integrally molded silicone laminate can be formed. Accordingly, it is useful as a marking ink material and a three-dimensional logo material for a silicone resin base material used for decorative objects such as key tops made of silicone rubber, especially for decoration marks and logos for clothes and shoes.

Claims (6)

(A) (A-1) an organopolysiloxane containing two or more aliphatic unsaturated groups bonded to a silicon atom in one molecule: 80 to 100 parts by weight (A-2) a hydrogen atom bonded to a silicon atom Organic compound containing one or more aliphatically unsaturated groups capable of hydrosilylation reaction in one molecule: 0 to 20 parts by weight (A-1) + (A-2), the amount of which is 100 parts by weight in total (B) an organohydrogenpolysiloxane containing two or more hydrogen atoms bonded to a silicon atom in one molecule: the total number of moles of the aliphatically unsaturated groups in the components (A-1) and (A-2) ( Assuming that the ratio (b) / (a) of the number of moles (b) of the hydrogen atom bonded to the silicon atom contained in this component to the component (a) is (p), p satisfies 0.5 ≦ p ≦ 1.5 ( C) Catalyst for hydrosilylation reaction: Organopolysiloxane containing effective amount And the cured product of hexane composition (I),
(D) (D-1) an organopolysiloxane containing two or more aliphatic unsaturated groups bonded to a silicon atom in one molecule: 80 to 100 parts by weight (D-2) a hydrogen atom bonded to a silicon atom Organic compound containing one or more aliphatically unsaturated groups capable of hydrosilylation in one molecule: 0 to 20 parts by weight (D-1) + (D-2) amount of 100 parts by weight in total (E) an organohydrogenpolysiloxane containing two or more hydrogen atoms bonded to a silicon atom in one molecule: the total number of moles of the aliphatically unsaturated groups in the components (D-1) and (D-2) ( Assuming that the ratio (e) / (d) of the number of moles (e) of hydrogen atoms bonded to silicon atoms contained in the component to d) is q, q is such that 0.5 <q ≦ 20 (F). Catalyst for hydrosilylation reaction: Organopolysilo containing an effective amount A laminate of the cured product of the acid composition (II), the molar ratio p, q is a silicone laminate, which is a p <q. 2. The silicone laminate according to claim 1, wherein q / p ≧ 1.2. 3. The silicone laminate according to claim 1, wherein the component (A-2) and / or the component (D-2) are an organosilane and / or an organo (poly) siloxane having 2 to 20 silicon atoms. body. The silicone laminate according to any one of claims 1 to 3, wherein the component (E) contains an organohydrogenpolysiloxane having a molecular structure incompatible with (D-1). The silicone laminate according to any one of claims 1 to 4, wherein the organopolysiloxane composition (I) and / or the organopolysiloxane composition (II) contains a coloring agent. The silicone laminate according to any one of claims 1 to 5, which is for a design.