KR20210112352A - Interpenetrating network polymer composed of crosslinked organopolysiloxane and (meth)acrylic polymer and method for producing the same - Google Patents

Abstract

(A) 90-30 mass parts of organopolysiloxane crosslinked product, and (B) (meth)acrylic polymer 10-70 mass parts (however, (A), the total of (B) component consists of 100 mass parts.), , the product of the tensile strength (the product of the tensile strength (MPa) and the tensile elongation at break (%)) obtained by measurement according to ISO37 (JIS K 6251) of a sheet of 2 mm thickness containing no filler is 1,000 or more. The interstitial network polymer has both the high tensile elongation at break of the organopolysiloxane and the high tensile strength of the acrylic resin.

Description

Interpenetrating network polymer composed of crosslinked organopolysiloxane and (meth)acrylic polymer and method for producing the same

The present invention relates to a polymer having an interpenetrating network structure in which an organopolysiloxane crosslinked product and a (meth)acrylic polymer are crosslinked by entangled molecular chains with each other, and a method for producing the same.

Since organopolysiloxane is excellent in heat resistance, weather resistance, stability in a wide temperature range, electrical insulation, water repellency, low toxicity, and tactile feel, it is used as an additive or main agent for various applications. However, the organopolysiloxane polymer or crosslinked product has low tensile strength and hardness, and cannot be used as a molded article.

In order to increase the tensile strength of the organopolysiloxane polymer, various fillers such as silica are blended to make thermally crosslinkable silicone rubbers and room temperature curable silicone rubbers.

The tensile product is the product of tensile strength and tensile elongation at break, and is used as an indicator of the energy to break a material. The anti-long product of the cross-linked organopolysiloxane product is 20 to 200 without fillers, and the tensile strength is less than 2 MPa.

On the other hand, acrylic resin has advantages of high hardness, high tensile strength, transparency, gloss, and processability, and is used in applications such as paints, adhesives, and aquariums. However, since the acrylic resin having excellent tensile strength has a low tensile elongation at break of 2 to 7%, the product of tensile strength is low and is 100 to 500.

By alloying two or more types of resin, it is performed to make up for the fault of both resin, or to make the cost of resin cheap. During alloying, some properties such as ABS resin are improved in some cases, but in most cases, alloying is difficult to exceed the mechanical properties of the original resin in that the boundary portion due to phase separation cannot be sufficiently adhered. . In particular, there are few examples of alloying between resins with poor compatibility.

The cross-linked organopolysiloxane product and the acrylic polymer have opposite advantages and disadvantages in terms of tensile strength and tensile elongation at break, and it is expected to compensate for each other’s shortcomings by alloying, but the cross-linked organopolysiloxane product and the acrylic polymer are compatible This is bad, and two layers are separated.

The mutual penetration network polymer is also referred to as an IPN resin, and has a structure in which the other resin chain passes through a cross-linked network of one resin. Due to this structure, even resins having poor compatibility can exist as a homogeneous polymer without being separated.

In general, the interpenetrating network polymer is made by polymerizing a first polymer to form a first network, followed by polymerizing a second polymer.

However, the organopolysiloxane and the acrylic polymer have poor compatibility and are immediately separated into two layers even when mixed. For this reason, there are few reported examples of interpenetrating network polymers composed of organopolysiloxane and acrylic polymer.

As reports on mutual penetration network polymers, there are Japanese Patent Application Laid-Open No. 2014-28919, Japanese Patent No. 3993143, and Japanese Patent Application Laid-Open No. 2017-95722 (Patent Documents 1 to 3).

Japanese Patent Application Laid-Open No. 2014-28919 (Patent Document 1) discloses a resin composite material in which molecular chains of a resin and a silane polymer such as silsesquioxane form an IPN structure, and preferred resins include polyolefin, polyamide, and polystyrene. , polycarbonate, polyurethane, ABS resin, and examples are melted 100 parts by mass of the resin and 10 to 40 parts by mass of 3-glycidoxypropyltriethoxysilane or vinyltriethoxysilane in laboplastomiil After kneading and reacting a vinyl group or a glycidoxy group with a resin, the sheet is formed by press working, and the alkoxy group is condensed by immersion in warm water at 80°C for 24 hours.

In this production method, the condensation reaction of silane is required for a long time, but in the condensation reaction with warm water, the degree of reaction progress is different from the outside and inside of the resin, and curing of the inside may be insufficient. Moreover, although evaluation is confirming IPN formation by looking at the viscoelasticity and coefficient of linear expansion, the mechanical characteristic is not measured.

Japanese Patent No. 3993143 (Patent Document 2) relates to a method for producing a semi-IPN composite, wherein a crosslinking agent containing a terminal silanol group-containing polysiloxane and a trialkoxysilane having an ammonium salt structure and a radically polymerizable monomer are mixed and polymerized. has been proposed.

This use is for a paint that inhibits the adhesion of marine organisms, and the semi-IPN structure has a biological adhesion repelling activity. Also, there is no description regarding the mechanical properties of the resin.

Japanese Patent Application Laid-Open No. 2017-95722 (Patent Document 3) discloses a hydrous polymer gel material for a molded medical material having properties of two types of polymers constituting a polymer gel having a network structure, which is an isocyanate group such as a cellulose derivative A reactive polymer and a polymer copolymerizable with a (meth)acrylic group or a vinyl group are crosslinked by a (meth)acrylic acid derivative or a vinyl derivative having an isocyanate group.

In this polymer gel material, the highest anti-long product in Examples is not as high as 550.

As described above, there is no report on a polymer having a cross-penetrating network structure of an organopolysiloxane crosslinked product having excellent mechanical properties and a (meth)acrylic polymer.

Japanese Patent Application Laid-Open No. 2014-28919 Japanese Patent No. 3993143 Japanese Patent Application Laid-Open No. 2017-95722

The present invention has been made in view of the above circumstances, and a cross-penetrating network polymer composed of an organopolysiloxane crosslinked product and (meth)acrylic polymer having both the high tensile elongation at break of the organopolysiloxane and the high tensile strength of the acrylic resin; And it aims to provide the manufacturing method.

As a result of repeated intensive studies in order to achieve the above object, the inventors of the present invention, after containing (b) (meth)acrylic monomer in (A) organopolysiloxane crosslinked product, polymerize (meth)acryl group to (B) (meth) ) to obtain an acrylic polymer, or (b) in a solution containing a (meth)acrylic monomer, (a1) an alkenyl group-containing organopolysiloxane and (a2) an organohydrogenpolysiloxane are subjected to an addition reaction to react (A) an organopolysiloxane 90-30 parts by mass of (A) an organopolysiloxane crosslinked product and (B) (B) (B) ( The mutual penetration network polymer consisting of 10 to 70 parts by mass of the meth)acrylic polymer (however, the total of the components (A) and (B) is 100 parts by mass.) is evaluated according to ISO37, even though no filler is blended. As a method, the long product obtained by measuring using a sheet of 2 mm thickness is 1,000 or more, and it has been found that mechanical properties are significantly improved compared to the prior art, and the present invention has been achieved.

Accordingly, the present invention provides the following interpenetrating network polymer and a method for producing the same.

One.

(A) 90-30 mass parts of organopolysiloxane crosslinked product, and (B) (meth)acrylic polymer 10-70 mass parts (however, (A), the total of (B) component consists of 100 mass parts.), , the product of the tensile strength (the product of the tensile strength (MPa) and the tensile elongation at break (%)) obtained by measurement according to ISO37 (JIS K 6251) of a sheet of 2 mm thickness containing no filler is 1,000 or more. Interstitial Reticulum Polymers.

2.

The mutual interpenetrating network polymer according to 1, wherein the tensile strength obtained by measurement according to ISO37 of a 2 mm thick sheet containing no filler is 3 MPa or more and the tensile elongation at break is 300% or more.

3.

The interpenetrating network polymer according to 1 or 2, wherein the (A) organopolysiloxane crosslinked product is an addition reaction product of (a1) an alkenyl group-containing organopolysiloxane and (a2) an organohydrogenpolysiloxane.

4.

(a2) The interpenetrating network polymer according to 3, wherein the organohydrogenpolysiloxane contains a (meth)acryl group.

5.

(A) The cross-penetrating network polymer according to any one of 1 to 4, wherein (B) (meth)acrylic polymer is obtained by containing (b) (meth)acrylic monomer in crosslinked organopolysiloxane and polymerizing (meth)acrylic group. manufacturing method.

6.

(b) In a solution containing a (meth)acrylic monomer, (a1) an alkenyl group-containing organopolysiloxane and (a2) an organohydrogenpolysiloxane are subjected to an addition reaction to obtain (A) an organopolysiloxane crosslinked product, after which ( The method for producing the interpenetrating network polymer according to any one of 1 to 4, wherein the (B) (meth)acrylic polymer is obtained by polymerizing a meth)acrylic group.

7.

The method for producing the interpenetrating network polymer according to 5 or 6, wherein the (meth)acryl group is polymerized by UV irradiation.

The interpenetrating network polymer of the present invention has excellent tensile strength and tensile elongation at break, and has a product of tensile strength of 1,000 or more, and has a high product of resistance that is impossible without a large amount of fillers as in the prior art. For this reason, it becomes possible to make a molded article stronger than a conventional (meth)acrylic resin, a sealant that is difficult to break and is not easily broken.

Hereinafter, the present invention will be described in more detail.

The mutual penetration network polymer of the present invention contains (A) 90 to 30 parts by mass of the organopolysiloxane crosslinked product and (B) 10 to 70 parts by mass of the (meth)acrylic polymer (provided that the total of components (A) and (B) is 100 is the mass part).

(A) As for the compounding ratio of component and (B) component, (B) component is 10-70 mass parts with respect to (A) component 90-30 mass parts, Preferably (A) component is 80-50 mass parts About this, (B)component is 20-50 mass parts, and (A)component + (B)component =100 mass parts at this time. When the component (A) is too large (when component (B) is too small), the tensile strength may be too low, and when component (A) is too small (when component (B) is too large), the tensile elongation at break is too low there is

<(A) component>

(A) A component is an organopolysiloxane crosslinked product. The method for synthesizing the present organopolysiloxane crosslinked product includes condensation, peroxide crosslinking, UV crosslinking, and addition reaction. Among them, an addition reaction type having a short reaction time is preferable.

Specifically, an addition reaction type organopolysiloxane crosslinked product is prepared by mixing the following components (a1), (a2) and (c) to prepare an addition reaction type organopolysiloxane composition, and then heat curing the composition. can be manufactured.

(a1) component is an alkenyl group-containing organopolysiloxane, the weight average molecular weight represented by the following general formula (1) is 800 or more and 80,000 or less, and the vinyl value is 0.003 mol/100g or more and 0.7 mol/100g or less, alkenyl in the molecule It is preferable that it is an organopolysiloxane which has two or more groups.

(Wherein, M is _{R 3 SiO 1/2, M} vi is R ₂ KSiO _1/2, D is _{R 2 SiO 2/2, D} vi is RKSiO _2/2, T has RSiO _3/2, T ^vi is KSiO _{3 /2} , Q is SiO _{4 /2} , R is each independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms that does not have an aliphatic unsaturated bond, and K is -(CH ₂ ) _L -CH=CH ₂ (L is a positive number of 0 or 6 or less) is an alkenyl group, d, e, g, and i are each independently 0 or a positive number exceeding 0, and e, g, and i are 0 at the same time 2≤e+g+i≤500, f is a positive number between 10 and 1,000, h is a positive number of 0 or 20 or less, and j is 0 or a positive number of 10 or less)

In the formula (1), each R is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms and not having an aliphatic unsaturated bond, preferably having 1 to 10 carbon atoms, particularly carbon The number of atoms is preferably 1 to 8, and specifically, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, and an octyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group and a tolyl group, a benzyl group, a phenene group Aralkyl groups, such as a tyl group, etc. are mentioned, Furthermore, halogen atom-substituted alkyl groups, such as a chloropropyl group and trifluoropropyl group, which substituted some or all of these hydrogen atoms with halogen atoms etc. are mentioned. As R, a methyl group and a phenyl group are preferable.

Further, as an alkenyl group represented by -(CH ₂ ) _L -CH=CH ₂ (L is a positive number of 0 or 6 or less) of K, specifically, a vinyl group, an allyl group, a butenyl group, a propenyl group, and 5-hexenyl group group, octenyl group, etc. are mentioned, Among these, a vinyl group is preferable.

In formula (1), d, e, g, and i are each independently 0 or a positive number exceeding 0, d is preferably 0 or 100 or less, and e is preferably 0 or 100 or less, It is preferable that g is 0 or a positive number of 500 or less, and it is preferable that i is 0 or a positive number of 100 or less. e, g, and i do not simultaneously become 0, and e+g+i is a positive number of 2 or more and 500 or less, Preferably it is a positive number of 2 or more and 200 or less.

Equation (1) to D (R ₂ SiO _2/2 structure) units f is a positive number in a range from 10 to 1,000, preferably a positive number of less than 40 800, more preferably in a range from 100 to 600 in is positive When f is less than 10, the tensile elongation at break may become too low. Moreover, when f becomes more than 1,000, hardness may become low too much.

h in Formula (1) is 0 or 20 or less positive number, Preferably it is 0 or 10 or less positive number, j is 0 or 10 or less positive number, Preferably it is 0 or 5 or less positive number.

As a vinyl value of the alkenyl group containing organopolysiloxane represented by Formula (1), they are 0.00105 mol/100g or more and 0.7 mol/100g or less, 0.005 mol/100g or more and 0.5 mol/100g or less are preferable, More preferably, they are 0.005 mol/100g. It is more than 0.3 mol/100g or less. When a vinyl value is less than 0.003 mol/100g, hardness may become low too much. Moreover, when the vinyl value is 0.7 mol/100g or more, the tensile elongation at break may become low too much.

The weight average molecular weights of the alkenyl group containing organopolysiloxane represented by Formula (1) are 800 or more and 80,000 or less, Preferably they are 3,000 or more and 60,000 or less, More preferably, they are 5,000 or more and 40,000 or less. When the weight average molecular weight is lower than 800, the tensile elongation at break may become too low. Moreover, when it is higher than 80,000, hardness may become low too much. In addition, in this invention, a weight average molecular weight is the ^{value calculated|required by 29} Si-NMR (the same hereafter).

Formula (1) a kinematic viscosity of a 25 ℃ of the alkenyl group-containing organopolysiloxane represented by is preferably in the range of 7 ~ 30,000mm ² / s, more preferably 100 ~ 3,000mm ² / s. In addition, in this invention, kinematic viscosity is the value measured with the Ostwald viscometer (it is the same hereafter).

As the alkenyl group-containing organopolysiloxane represented by the above formula (1), specifically, siloxane containing both terminal alkenyl groups, siloxane containing side chain alkenyl groups, siloxane containing both terminal and side chain alkenyl groups, and siloxane containing both terminals and side chain alkenyl groups , branched terminal alkenyl group-containing siloxane, and the like.

In terms of structural formula, M ^Vi ₂ D _f , M ₂ D _f D ^Vi _g , M ^Vi ₃ D _f T ₁ , M ^Vi ₄ D _f T ₂ , M ^Vi ₂ D _f D ^Vi _g , M ^Vi ₂ D _f Q ₁ , M _α D _f D ^Vi _g T ^Vi _i (M, M ^vi , D, D ^Vi , T, T ^vi , Q, f, g, and i are the same as described above. Hereinafter, the same) and the like. Moreover, as a specific structural example, M ^Vi ₂ D ₁₀₀ , M ₂ D ₉₇ D ^Vi ₃ , M ₂ D ₂₆ D ^Vi ₄ , M ₂ D ₉₆ D ^Vi ₄ , M ₂ D ₉₅ D ^Vi ₅ , M ^Vi ₃ D ₁₀₀ T _{1 .} , M ^Vi ₄ D ₁₀₀ T ₂ , M ^Vi ₂ D ₉₇ D ^Vi ₁ , M ^Vi ₂ D ₉₅ D ^Vi ₃ , M ₃ D ₉₃ D ^Vi ₃ T ^Vi ₁ , M ^Vi ₂ D ₁₅₀ , M ^Vi ₂ D ₁₀₀₀ , M ₂ D ₉₀₀ D ^Vi ₂₀ and the like.

(a2) component is an organohydrogenpolysiloxane, the kinematic viscosity at 25°C is 2 mm ² /s or more and 500 mm ² /s or less, and is an organ having at least two hydrogen atoms (SiH groups) bonded to silicon atoms in one molecule. It is preferable that it is ganohydrogenpolysiloxane. When the SiH group of the organohydrogenpolysiloxane of the component (a2) and the alkenyl group of the alkenyl group-containing organopolysiloxane of the component (a1) are subjected to an addition reaction, an organopolysiloxane crosslinked product (A) is formed.

(a2) component WHEREIN: Preferably the hydrogen atom (SiH group) couple|bonded with the silicon atom in 1 molecule is 2-100 pieces, More preferably, it is 4-80 pieces.

Moreover, as SiH group content of (a2) component, 0.0021-3.5 mol/100g is preferable, More preferably, it is 0.01-2.5 mol/100g, More preferably, it is 0.02-2.0 mol/100g. When the SiH group content is too small, the curing property may deteriorate, and when the SiH group content is too large, the tensile elongation at break may become too low.

(a2) It is preferable that the kinematic viscosity in 25 degreeC of a component is 2 mm ² /s or more and 500 mm ² /s or less, More preferably, they are 2 mm ² /s or more and 300 mm ² /s or less, More preferably, they are 5 mm ² /s. More than 200 mm ² /s or less. When the kinematic viscosity is ^{less than 2} mm 2 /s, the tensile elongation at break may be too low. Moreover, when it is higher than 500 mm<^2> /s, curing property may worsen. In addition, in this invention, kinematic viscosity can be measured with an Ostwald viscometer.

Moreover, the organohydrogenpolysiloxane of (a2) component may contain a (meth)acryl group, and when it contains a (meth)acryl group, this (meth)acryl group in the (meth)acryl monomer of (b) component (meth)acryl group ) It can be polymerized with an acryl group to obtain a polymer having a strong mutual interpenetration network structure.

When it has a (meth)acryl group, as for the content, 0.016-1.6 mol/100g is preferable, More preferably, it is 0.02-1.0 mol/100g. If the (meth)acryl group content is too small, it may not react with the acrylic monomer and the mechanical strength may not be changed.

As organohydrogenpolysiloxane of (a2) component, it is preferable to have a structure represented by following General formula (2).

(Wherein, M ^U is _{R 2 VSiO 1/2, M} H is _{R 2 HSiO 1/2, D} U is RVSiO _2/2, D ^H is RHSiO _2/2, T ^U is VSiO _3/2, T ^H is HSiO _{3 /2} , Q is SiO _{4 /2} , and R is each independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms and not having an aliphatic unsaturated bond. V is R or -(CH ₂ ) _L -O-(CO)-CW=CH ₂ (L is 0 or a positive number less than or equal to 6, and W is H or a methyl group.) m, n, o, q each independently represent 0 or 0 is a positive number exceeding, p is a positive number from 2 to 100, r is a positive number 0 or 10 or less, s is a positive number 0 or 10 or less, n, p, and r do not simultaneously become 0, 2≤n+ p+r≤100.)

In the formula (2), R is each independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms that does not have an aliphatic unsaturated bond, and the same as R in formula (1) can be exemplified. and among these, a C1-C8 alkyl group is preferable.

In formula (2), m, n, o, and q are each independently 0 or a positive number exceeding 0, m is preferably 0 or 10 or less, and n is preferably 0 or 10 or less, It is preferable that o is 0 or a positive number of 100 or less, and it is preferable that q is 0 or a positive number of 10 or less. Further, p is a positive number of 2 to 100, preferably a positive number of 4 to 80, r is a positive number of 0 or 10 or less, preferably 0 or 5 or less, s is 0 or a positive number of 10 or less, preferably is a positive number less than or equal to 0 or 5. Moreover, n+p+r is a positive number of 2-100, Preferably it is a positive number of 4-80.

It is preferable that the weight average molecular weights of this organohydrogenpolysiloxane are 194-10,000, More preferably, it is 874-8,500. When the weight average molecular weight is too small, the tensile elongation at break may become too low, and when it is too large, the reactivity may worsen and the cure property may fall.

As the organohydrogenpolysiloxane of the component (a2), specifically, siloxane containing both terminal hydrogensilyl groups, siloxane containing side chain hydrogensilyl groups, siloxane containing single terminal and side chain hydrogensilyl groups, both terminals and side chain hydroxanes Rosensilyl group containing siloxane etc. are mentioned.

Expressed by the following structural ^{_{formula, M H 2 D o, M}} 2 D H p, M 2 D o D H p, M H 2 D o D H p, M H 3 D o T 1, M H 4 D o T 2, M _m D _o D ^H _p T ^H _r (M, M ^H , D, D ^H , T, T ^H , Q, m, o, p, r are the same as above. Hereinafter the same.) and the like. Further, as specific structural examples, M ^H ₂ D ₁₀ , M ^H ₂ D ₁₀₀ , M ₂ D ₂₇ D ^H ₃ , M ₂ D ₉₇ D ^H ₃ , M ₂ D ₂₆ D ^H ₄ , M ₂ D ₂₅ D ^H ₅ , M ₂ D ₂₄ D ^H ₆ , M ₂ D ₉₆ D ^H ₄ , M ₂ D ₉₅ D ^H ₅ , M ^H ₃ D ₁₀₀ T ₁ , M ^H ₄ D ₁₀₀ T ₂ , M ^H ₂ D ₉₇ D ^H ₁ , M ^H ₂ D ₉₅ D ^H ₃ , M ₃ D ₉₃ D ^H ₃ T ^H ₁ , M ^U' ₂ D ₂₇ D ^H ₃ , M ^U' ₂ D ₉₅ D ^H _{5 ,} etc. (M ^U' is R ₂ V 'a SiO _1/2, V' is - (CH ₂₎ represents a _{3 -O- (CO) -C (CH} 3) = CH 2)..

(a2) The compounding quantity of component is the quantity used as the range of 0.5-5 mol of the hydrogen atom (SiH group) couple|bonded with the silicon atom with respect to 1 mol of the alkenyl groups of (a1) component. This corresponds to 0.00105 to 0.7 mol/100 g as the amount of alkenyl groups and 0.0021 to 3.5 mol/100 g as the amount of SiH functional groups. When there are too many (a2) components, a crosslinking density will be low, and it may become a structure with a large intensity|strength weak crosslinking network structure, and when there are too few, curing property will become inadequate.

<(c) Platinum Group Metal-Based Catalyst>

(c) component is a platinum group metal type catalyst, and the well-known thing used as an addition reaction catalyst can be used. As such a platinum group metal catalyst, catalysts, such as a platinum type, a palladium type, a rhodium type, a ruthenium type, are mentioned, for example, Among these, a platinum type catalyst is used especially preferably. Examples of the platinum-based catalyst include chloroplatinic acid, an alcohol solution or an aldehyde solution of chloroplatinic acid, a complex of chloroplatinic acid with various olefins or vinylsiloxane, and a complex of platinum with various olefins or vinylsiloxane.

(c) The amount of the platinum group metal catalyst added is not particularly limited as long as it is a catalytically effective amount, but the mass of the composition (for example, (a1), (a2), (b), (c) component, and (d), (e) described later ) Platinum group metal mass (Platinum group metal mass ÷ total composition mass ((a1) + (a2) + (b) + (c) + (d) + (e)) with respect to the total mass of the component) is 1 to 200 ppm, especially It is preferable that it is 5-100 ppm.

<(d) Addition Reaction Control Agent>

(d) The addition reaction control agent of the component is a component that is blended as needed, and controls the catalytic activity of the platinum group metal catalyst, and various organic nitrogen compounds, organophosphorus compounds, acetylenic compounds, oxime compounds, organic chloro compounds, etc. can be heard Specifically, 1-ethynyl-1-cyclohexanol, 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 3-methyl-1-pentene-3- Acetylene-based alcohols such as ol and phenylbutynol, acetylenic compounds such as 3-methyl-3-1-pentene-1-yne and 3,5-dimethyl-1-hexyne-3-yne, 1,1-dimethylpropyne A reaction product of an acetylene-based compound such as nyloxytrimethylsilane and alkoxysilane, siloxane or hydrogensilane, vinylsiloxane such as tetramethylvinylsiloxane cyclic, organic nitrogen compounds such as benzotriazole, and other organophosphorus compounds, oxime compounds , a maleic acid compound, an organic chromium compound, and the like.

In the case of blending the addition reaction controlling agent (d), the blending amount is as long as good treatment bath stability is obtained, and is generally 0.01 to 5 parts by mass, preferably 0.01 to 5 parts by mass based on 100 parts by mass in total of the component (A) and component (B). It is 0.1-3 mass parts.

As described above, the cross-linked organopolysiloxane of the addition-reaction type is prepared by mixing the component (a1), component (a2), component (c), and component (d) if necessary to obtain an addition-reaction type organopolysiloxane composition. After preparing the composition, it can be produced by heating and curing the composition at 20 to 200° C., particularly 40 to 150° C. for 10 seconds to 2 hours, particularly 1 minute to 1.5 hours.

Further, since the cross-linked organopolysiloxane of the addition reaction type has flexibility, the reaction rate between the component (a1) and the component (a2) is preferably 90% or more, and more preferably 93 to 100%. In addition, the said reaction rate can be computed by measuring the amount of hydrogen gas generation.

How to calculate the amount of hydrogen gas generated;

5 to 10 g of the organopolysiloxane crosslinked product and the organopolysiloxane composition are each put in a Meyer, diluted with about 10 g of n-butanol, and set in a gas burette. The solution is stirred with a stirrer. 20 ml of 20 mass % NaOH aqueous solution is thrown into the dropping funnel, and it is dripped at Meyer. After stirring for 10 minutes, hydrogen gas is obtained from the following formula.

Hydrogen gas generation amount (ml/g) = [value of hydrogen gas generation amount on scale ml/g] × 273 ÷ (temperature (°C) + 273) × atmospheric pressure (hPa) ÷ 1013 (hPa)

How to find the response rate;

It is calculated|required by the following formula from the said hydrogen gas generation amount.

Reaction rate (%) = {1-(Hydrogen gas generation amount (ml/g) of organopolysiloxane crosslinked product (composition after reaction) ÷ Hydrogen gas generation amount (ml/g) of organopolysiloxane composition (composition before reaction))}× 100

<(B) component>

(B) A component is a (meth)acrylic polymer, and is obtained by superposing|polymerizing the (b) (meth)acryl monomer. (b) The (meth)acryl monomer includes a compound having one (meth)acryl group and a compound having two or more (meth)acryl groups.

(b) The compound containing the (meth)acryl group among the (meth)acryl monomers has a weight average molecular weight of 72-1,000, It is preferable that it is what is represented by following formula (3).

(Wherein, R ¹ is a hydrogen atom or a methyl group, Y is an oxygen atom or NR ² (R ² is a hydrogen atom or R), wherein R is an unsubstituted C1-C12 aliphatic unsaturated bond. or a substituted monovalent hydrocarbon group, a is an integer of 1-4, and Z is an organic group of 1-4.)

In the formula (3), Y is an oxygen atom or NR ² (R ² is a hydrogen atom or R). Here, R is a C1-C12 unsubstituted or substituted monovalent hydrocarbon group which does not have an aliphatic unsaturated bond, The thing similar to what was illustrated as R in the said Formula (1) can be illustrated.

a is an integer of 1-4, Preferably it is an integer of 1-3.

Z is a 1-4 valent organic group, and when a is 4, it is preferable that Z is a carbon atom. When a is 3, Z is (-CH _{2) 3} CR is preferred (R is the same as the aforementioned.), a trivalent group of the number of carbon atoms from 2 to 12 and the like. When a is 2, Z is an alkylene group having 1 to 30 carbon atoms, an arylene group having 6 to 30 carbon atoms, a bisphenylene group, a fluorene group, an oxyalkylene group having 2 or 3 carbon atoms, or a carbon atom It is preferable that it is a polyoxyalkylene group of 4-20, and even if a hydroxyl group, an epoxy group, and an isocyanate group exist in a part, it is not cared about. When a is 1, Z is a hydrogen atom, a ureido group, a glycidyl group, a tetrahydrofurfuryl group, or a carbon atom which may have an ether bond, a carbonyl bond or an ester bond interposed therebetween, and which may be substituted with fluorine or hydroxy. It is preferable that it is a number 1-30, Preferably it is a monovalent hydrocarbon group of 1-24.)

Here, the alkylene group having 1 to 30 carbon atoms is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and specific examples thereof include methylene, ethylene, propylene, trimethylene, n -Butylene, isobutylene, s-butylene, n-octylene, 2-ethylhexylene, n-decylene, n-undecylene, n-dodecylene, n-tridecylene, n-tetradecylene , n-pentadecylene, n-hexadecylene, n-heptadecylene, n-octadecylene, n-nonadexylene, n-eicosanylene group, 1,4-cyclohexylene group, tricyclodecanedi A methylene group etc. are mentioned.

The arylene group having 6 to 30 carbon atoms is preferably an arylene group having 6 to 12 carbon atoms, and specific examples thereof include o-phenylene, m-phenylene, p-phenylene, 1,2-naphthylene, 1 ,8-naphthylene, 2,3-naphthylene, 4,4'-biphenylene group, and the like.

Examples of the oxyalkylene group include an oxyethylene group, an oxypropylene group, and an oxybutylene group, and examples of the polyoxyalkylene group include a polyoxyethylene group, a polyoxypropylene group, and a polyoxybutylene group.

Moreover, a hydroxyl group, an epoxy group, and an isocyanate group may exist in some hydrogen atoms of these groups.

Examples of the monovalent hydrocarbon group having 1 to 30 carbon atoms, preferably 1 to 24 carbon atoms, 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, and a neophene. Tyl group, hexyl group, cyclohexyl group, octyl group, ethylhexyl group, decyl group, isodecyl group, sec-decyl group, tert-decyl group, neodecyl group, cyclodecyl group, lauryl group, stearyl group, behe Alkyl groups such as nyl group, norbornyl group, isobornyl group, adamantyl group and dicyclopentanyl group, alkenyl group such as vinyl group, allyl group and propenyl group, phenyl group, tolyl group, xylyl group, and naphthyl group , an aralkyl group such as a benzyl group, a phenylethyl group, or a phenylpropyl group, and those in which some or all of the hydrogen atoms of these groups are substituted with a fluorine atom or a hydroxy group. In addition, these monovalent hydrocarbon groups may have an ether bond, a carbonyl bond, or an ester bond interposed therebetween.

(b) As a compound containing one (meth)acryl group among (meth)acryl monomers, the following compound is mentioned as a specific example.

2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, 4-hydroxybutyl acrylate, acrylic acid, butyl acrylate, methyl acrylate, ethyl acrylate, tert-butyl acrylate, iso Butyl acrylate, methacrylic acid, isodecyl acrylate, stearyl acrylate, behenyl acrylate, lauryl acrylate, ethyl diglycol acrylate, propyl heptyl acrylate, dicyclopentanyl acrylate, isobornyl acrylate, Cyclohexyl methacrylate, tert-butyl methacrylate, ureido methacrylate, lauryl methacrylate, stearyl methacrylate, behenyl methacrylate, tetrahydrofurfuryl methacrylate, benzyl methacrylate, Phenoxyethyl methacrylate, isobornyl methacrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate, 2-methacryloyloxyethyl succinic acid, trifluoroethyl methacrylate.

Moreover, as a compound containing two or more (b) (meth)acryl groups in a (meth)acryl monomer, the following compound is mentioned as a specific example.

Tetraethylene glycol diacrylate, nonaethylene glycol diacrylate, tetradecanylethylene glycol diacrylate, tricyclodecane dimethanol diacrylate, 1,10-decanediol diacrylate, 1,6-hexanediol diacrylate Rate, 1,9-nonanediol diacrylate, dipropylene glycol diacrylate, heptapropylene glycol diacrylate, trimethylolpropane triacrylate, tetraethylene glycol dimethacrylate, nonaethylene glycol dimethacrylate, tetra Decanylethylene glycol dimethacrylate, tricyclodecanedimethanol dimethacrylate, 1,10-decanediol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate rate, dipropylene glycol dimethacrylate, heptapropylene glycol dimethacrylate, trimethylolpropane trimethacrylate, glycerin dimethacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate.

(b) As a (meth)acrylic monomer, especially, since isobornyl acrylate has compatibility with an organopolysiloxane crosslinked product slightly better than other acryl monomers, it is preferable.

(b) Polymerization of (meth)acryl monomer can be performed using (e) a radical initiator. In addition, polymerization of (b) (meth)acrylic monomer is polymerized by containing (b) component in (A) component, or (a1), (a2) and (b) component are mixed in advance, (a1), ( After adding a2) component, it is preferable to polymerize (b) component.

<(e) radical initiator>

(e) A radical initiator is a component blended in order to polymerize a (meth)acryl monomer, and is a compound which decomposes|disassembles by heat or light irradiation, and generates a radical. A (meth)acryl group is superposed|polymerized by the generated radical.

A known radical initiator can be used, for example, organic peroxide, dihalogen, azo compound, redox catalyst, triethylborane, diethylzinc, alkylphenone-based photopolymerization initiator, acylphosphonic oxide-based photopolymerization initiator, intramolecular A hydrogen extraction type photoinitiator, an oxime ester type|system|group photoinitiator, the blend of several photoinitiators, etc. are mentioned.

(e) Generally, it is preferable that the compounding quantity of a radical initiator is 0.01-25 mass parts with respect to 100 mass parts of the sum total of (A) component and (b) component (or the sum total of (a1), (a2), and (b) component) And more preferably, it is 0.1-15 mass parts, More preferably, it is 1-10 mass parts. (e) When there are too few components, superposition|polymerization of (b) component may not advance, and when there are too many, stop reaction occurs easily and polymerization degree may become low.

[Optional Ingredients]

In the production of the mutually penetrating network polymer of the present invention, other components may be added as needed within a range that does not impair the purpose and effect of the present invention. Moreover, even when diluted with an organic solvent, the characteristic does not fall.

As the organic solvent, an organic solvent soluble in organopolysiloxane such as toluene, hexane, xylene and methyl ethyl ketone (siloxane solvent is not included), low-viscosity cyclic siloxane such as octamethyltetrasiloxane and decamethylpentasiloxane, M _{2D n} (M and D are the same as above. n is a positive number of 0 or 200 or less, preferably a positive number of 1-50.) straight-chain siloxane, such as M _2+m D _n T _m (M, D , T is the same as above. n is 0 or a positive number of 200 or less, preferably a positive number of 1 to 50, m is a positive number of 1 to 10, preferably a positive number of 1 to 3.) Branched chain siloxanes such as It is preferable to use organopolysiloxane (siloxane solvent), such as these.

The usage-amount of a solvent is 0-50 of the total (or the sum total of (a1), (a2), and (b) component) mass of the organopolysiloxane crosslinked product of (A) component and the (meth)acrylic monomer of (b) component It is preferable that it is a double, and it is especially preferable that it is 8-30 times.

In addition, high molecular weight hydrocarbons, high molecular weight linear organopolysiloxane, silicone resin having an aryl group, silicone resin, silica, silicone powder, fillers such as talc or mica to increase mechanical strength, and compatibilizing agent for the purpose of imparting slipperiness Acrylic silicone, etc. can be added as needed. In addition, the addition amount of an arbitrary component can be made into a normal amount in the range which does not impair the effect of this invention.

[Preparation of interpenetrating network polymer]

Preparation of the mutual penetration network polymer of the present invention, for example, by mixing the above component (A), component (b) and component (e), (meth)acryl group of component (b), and component (A) In the case of having a (meth)acryl group, the mutual penetration network polymer can also be prepared by polymerizing these (meth)acryl groups to obtain the component (B), but the components (a1), (a2) and (b) Further, a composition for interpenetrating network polymer in which components (c) and (e) and, if necessary, component (d) and other components are mixed in advance, is prepared, and components (a1) and (a2) in this composition are added After making it react to obtain (A) component, when it has a (meth)acrylic group in the (meth)acryl group of (b) component, and (A) component, these (meth)acryl groups are polymerized, and (B) component It is preferable to prepare a mutually penetrating network polymer by obtaining it.

In this case, it is preferable to add (c)component after mixing the above-mentioned (a1), (a2), (b), (d), (e) component and arbitrary component uniformly beforehand. Each component may be used by a single type, and may use 2 or more types together.

In addition, when polymerizing (A) and (B) component after mixing (a1), (a2) and (b) component, the mixing ratio of these (a1) component, (a2) component, and (b) component is (a1) ) and the sum total of (a2) component: It is preferable that (b) component is 90:10-30:70 by mass ratio, More preferably, it is 80:20-50:50.

Kinematic viscosity of a 25 ℃ of the resulting interpenetrating polymer network for compositions and to 3,000mm ² / s or less, and more preferably 100 ~ 2,000mm ² / s, more preferably of 150 ~ 1,500mm ² / s . When the kinematic viscosity is too low, the tensile elongation at break may become too low. When it is too high, the curing property may deteriorate.

As addition reaction conditions of the (a1) and (a2) components in the said preparation method, it is 20-180 degreeC, especially 40-150 degreeC, It is 10 minutes - 3 hours, It is preferable to set it as 30 minutes - 2 hours especially.

In addition, polymerization of the (meth)acryl group of (b) component, or this and the (meth)acryl group in (A) component can be performed by UV irradiation, and specifically, as this polymerization condition, the wavelength of 200-500 nm Irradiate light for 1 to 60 seconds using UV light. In addition it is the accumulated light quantity is more preferably 2,000 ~ 10,000mJ / cm ² in that the preferably, 3,000 ~ 8,000mJ / cm ^2.

In the interpenetrating network polymer of the present invention obtained in this way, the tensile strength product (tensile strength (MPa) and tensile elongation at break (%)) obtained by measurement according to ISO37 (JIS K 6251) of a 2 mm thick sheet containing no filler. The product of ) is 1,000 or more, preferably 1,000 to 10,000, and more preferably 1,000 to 5,000. If the long product is less than 1,000, the polymer becomes brittle. In addition, in the present invention, in order to set the long product to 1,000 or more, it is important to have both the flexibility of the silicone and the strength of the acrylic resin, and it is necessary that the addition reaction and the acrylic polymerization proceed sufficiently. As for the addition reaction, it is preferable that the reaction of the component (a1) and the component (a2) has a reaction rate of 90% or more, and for the acrylic polymerization, the nonvolatile content of the interpenetrating network polymer is preferably 90% or more.

The nonvolatile content of the interpenetrating network polymer is preferably 85% or more, and more preferably 90% or more. In addition, the said non-volatile content can be measured from the difference with the mass of the polymer before toluene extraction by measuring the mass of the residual polymer after toluene extraction and drying the obtained mutual penetration network polymer.

In addition, the tensile strength is preferably 3 MPa or more, particularly 3 to 20 MPa, and the tensile elongation at break is preferably 300% or more, particularly 300 to 1,000%.

The mutual interpenetration network polymer of the present invention has excellent tensile strength and tensile elongation at break, and has a long product of 1,000 or more, which was impossible without a large amount of fillers as in the prior art. It becomes possible to produce a single molded body, a brittle, non-brittle sealant, and the like. Specifically, it is useful as casings for electronic components, remote controls, personal computers, mobile phones, televisions, and the like.

(Example)

Hereinafter, the present invention will be specifically described by showing examples and comparative examples, but the present invention is not limited to the following examples. In addition, in the following example, the reaction rate is calculated by measuring the amount of hydrogen gas generated, the amount of hydrogen gas generated is measured by the method shown below, and the nonvolatile matter is a polymer in toluene of a mass equivalent to 100 times the mass of the polymer. After 1 day impregnation, toluene is removed, and the swollen polymer is dried at 100° C. for 1 hour, and can be obtained from the difference between the polymer mass and the polymer mass before toluene impregnation. Moreover, the weight average molecular weight of the organopolysiloxane used as the following raw material was calculated|required by ^{29 Si-NMR.}

How to measure the amount of hydrogen gas generated

5 to 10 g of the sample (composition for interpenetrating network polymer (composition after addition reaction) and composition for interpenetrating network polymer (composition before addition reaction) obtained by crosslinking component (a1) and component (a2)) into Meyer, It was diluted with about 10 g of n-butanol and set in a gas burette. The solution was stirred with a stirrer. 20 ml of 20 mass % NaOH aqueous solution was thrown into the dropping funnel, and it was dripped at Meyer. After stirring for 10 minutes, hydrogen gas was obtained from the following formula.

Hydrogen gas generation amount (ml/g) = [value of hydrogen gas generation amount on scale ml/g] × 273 ÷ (temperature (°C) + 273) × atmospheric pressure (hPa) ÷ 1013 (hPa)

How to Calculate Response Rate

It calculated|required by the following formula from the hydrogen gas generation amount obtained by the above-mentioned method.

Reaction rate (%) = {1-((a1) component and (a2) component cross-linked, hydrogen gas generation amount (ml/g) of interpenetration network polymer composition (composition after addition reaction) ÷ composition for mutual penetration network polymer ( The amount of hydrogen gas generated (ml/g)) of the composition before the addition reaction)}×100

[Example 1]

(a1) 87.5 parts by mass of methylvinylpolysiloxane (1) as a component, 12.5 parts by mass of methylhydrogenpolysiloxane (2) as a component (a2), 38 parts by mass of isobornyl acrylate (4) as a component (b), (d) ) 0.15 parts by mass of 1,1-dimethylpropynyloxytrimethylsilane as an addition reaction controlling agent component, (e) 4 parts by mass of Irgacure 1173 (2-hydroxy-2-methyl-1-phenylpropanone) as a radical initiator After adding and stirring until uniform, (c) a complex of platinum and vinylsiloxane as an addition reaction catalyst (a1), (a2), (b), (c), (d) and (e) With respect to the total mass of the components, added so as to be 15 ppm in terms of platinum atomic mass, stirred until uniform, and kinematic viscosity of 301 mm ² /s, H/Vi (ratio of SiH groups in the composition to alkenyl groups in the composition) = 1.1 A composition for a mutually penetrating network polymer was prepared.

After putting the composition into a fluorine-coated mold frame having a depth of 2 mm and an area of 15 cm × 20 cm, a fluorine-coated gold plate is placed therebetween, heated at 50° C. for 1 hour, and the organopolysiloxane (a1) component and (a2) ) component was crosslinked (reaction rate 94%). The organopolysiloxane cross-linked product containing this component (b) was treated with a metal halide lamp (wavelength: 200-500 nm, particularly 300-450 nm, with high output) under a nitrogen atmosphere using a UV irradiation device at 4,000 mJ/cm ² Acryl groups in the composition (in component (b)) were polymerized by UV irradiation with an accumulated light amount to synthesize a mutual penetration network polymer (nonvolatile content of the mutual penetration network polymer 90%).

[Example 2]

(a1) 86.1 parts by mass of methylvinylpolysiloxane (1) as component, 13.9 parts by mass of acrylic group-containing methylhydrogenpolysiloxane (3) as (a2) component, 43 parts by mass of isobornyl acrylate (4) as (b) component , (d) 0.15 parts by mass of 1,1-dimethylpropynyloxytrimethylsilane as an addition reaction controlling agent component, (e) 4 parts by mass of Irgacure 1173 as a radical initiator was added, followed by stirring until uniform ( c) 15 ppm of the complex of platinum and vinylsiloxane as an addition reaction catalyst in terms of platinum atomic mass with respect to the total mass of the components (a1), (a2), (b), (c), (d) and (e) It was added as much as possible and stirred until uniform ^{, to prepare a composition for interpenetrating network polymers having a kinematic viscosity of 273 mm 2} /s and H/Vi (ratio of SiH groups in the composition to alkenyl groups in the composition) = 1.1.

Preparation was carried out under the same conditions as in Example 1 (reaction rate of component (a1) and component (a2) was 96%), and a mutual interpenetration network polymer was synthesized (nonvolatile content of the mutual interpenetration network polymer 92%).

[Example 3]

(a1) 86.1 parts by mass of methylvinylpolysiloxane (1) as component, 13.9 parts by mass of acrylic group-containing methylhydrogenpolysiloxane (3) as (a2) component, 78.9 parts by mass of isobornyl acrylate (4) as (b) component , (d) 0.15 parts by mass of 1,1-dimethylpropynyloxytrimethylsilane as an addition reaction controlling agent component, and (e) 4 parts by mass of Irgacure 1173 as a radical initiator, followed by stirring until uniform ( c) 15 ppm of the complex of platinum and vinylsiloxane as an addition reaction catalyst in terms of the atomic mass of platinum with respect to the total mass of the components (a1), (a2), (b), (c), (d) and (e) It was added as much as possible and stirred until uniform ^{, to prepare a composition for interpenetrating network polymers having a kinematic viscosity of 158 mm 2} /s and H/Vi (ratio of SiH groups in the composition to alkenyl groups in the composition) = 1.1.

The preparation was carried out under the same conditions as in Example 1 (reaction rate of component (a1) and component (a2) was 96%), and a mutual interpenetration network polymer was synthesized (nonvolatile content of the interpenetration network polymer 93%).

[Comparative Example 1]

^{From Example 1, a composition having a kinematic viscosity of 807 mm 2} /s and H/Vi (ratio of SiH groups in the composition to alkenyl groups in the composition) = 1.1 was prepared in which isobornyl acrylate and Irgacure 1173 were removed.

After putting the composition into a fluorine-coated mold frame having a depth of 2 mm and an area of 15 cm × 20 cm, a fluorine-coated gold plate is placed therebetween, heated at 50° C. for 1 hour, and the organopolysiloxane (a1) component and (a2) ) components were crosslinked (reaction rate 95%).

-Description of raw materials used-

Methylvinylpolysiloxane (1)

Polysiloxane having both ends of the molecular chain blocked with dimethylvinylsiloxy groups and all but made of (CH ₃ ) ₂ SiO units, having a vinyl value of 0.013 mol/100 g, a kinematic viscosity of 1,000 mm ² /s, and a weight average molecular weight of 15,000

Methylhydrogenpolysiloxane (2)

Both ends of the molecular chain are blocked with trimethylsiloxy groups, the main chain _{consists of (CH 3} )HSiO units and (CH ₃ ) ₂ SiO units, the SiH group content is 0.1 mol/100 g, the kinematic viscosity is 110 mm ² /s, the weight average Methylhydrogenpolysiloxane having a molecular weight of 6,500

Methylhydrogenpolysiloxane (3)

Both ends of the molecular chain are blocked with _{acryldimethylsiloxy groups, the main chain is composed of (CH 3} )HSiO units and (CH ₃ ) ₂ SiO units, the SiH group content is 0.089 mol/100 g, the acrylic group content is 0.025 mol/100 g , methylhydrogenpolysiloxane having a kinematic viscosity of 130mm ² /s and a weight average molecular weight of 8,100

Isobornyl acrylate (4)

A compound represented by the following formula (4) (molecular weight 208.3, specific gravity 0.983 g/ml)

The results of the following mechanical property evaluation of the polymers of Examples and Comparative Examples are shown in Tables 1 and 2 together with the blending amount of the composition.

〔Hardness〕

It was measured using a type A durometer according to ASTM D 2240.

[Tensile strength and tensile elongation at break]

A 2 mm thick sheet was prepared for a punching test sample with a dumbbell of JIS No. 5, and was measured according to ISO37 (JIS K 6251) using AGS-X (manufactured by Shimadzu Corporation).

Claims (7)

(A) 90-30 mass parts of organopolysiloxane crosslinked product, and (B) (meth)acrylic polymer 10-70 mass parts (however, (A), the total of (B) component consists of 100 mass parts.), , the product of the tensile strength (the product of the tensile strength (MPa) and the tensile elongation at break (%)) obtained by measurement according to ISO37 (JIS K 6251) of a sheet of 2 mm thickness containing no filler is 1,000 or more. Interstitial Reticulum Polymers. The interpenetrating network polymer according to claim 1, wherein a tensile strength of 3 MPa or more and a tensile elongation at break of 300% or more obtained by measurement according to ISO37 of a 2 mm thick sheet containing no filler is obtained. The interpenetrating network polymer according to claim 1 or 2, wherein the cross-linked organopolysiloxane (A) is an addition reaction product of (a1) an alkenyl group-containing organopolysiloxane and (a2) an organohydrogenpolysiloxane. . The interpenetrating network polymer according to claim 3, wherein (a2) the organohydrogenpolysiloxane contains a (meth)acryl group. (A) The organopolysiloxane crosslinked product contains (b) (meth)acryl monomer, and (B) (meth)acrylic polymer is obtained by polymerizing (meth)acryl group, in any one of claims 1 to 4 A process for the preparation of the described interpenetrating network polymer. (b) In a solution containing a (meth)acrylic monomer, (a1) an alkenyl group-containing organopolysiloxane and (a2) an organohydrogenpolysiloxane are subjected to an addition reaction to obtain (A) an organopolysiloxane crosslinked product, and then ( The method for producing the interpenetrating network polymer according to any one of claims 1 to 4, wherein the (B) (meth)acrylic polymer is obtained by polymerizing meth)acryl groups. The method of claim 5 or 6, wherein the (meth)acryl group is polymerized by UV irradiation.