Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
  • C08F290/06—Polymers provided for in subclass C08G
  • C08F290/068—Polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/04—Acids; Metal salts or ammonium salts thereof
  • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
  • C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
  • C08F290/06—Polymers provided for in subclass C08G
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
  • C08L51/085—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds on to polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
  • C08L83/04—Polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/04—Polymer mixtures characterised by other features containing interpenetrating networks

Definitions

• the present invention relates to a polymer having an interpenetrating network structure in which a crosslinked product of an organopolysiloxane and a (meth)acrylic polymer are entangled and crosslinked with each other, and a method for producing the same.
• Organopolysiloxane has excellent heat resistance, weather resistance, stability in a wide temperature range, electrical insulation, water repellency, low toxicity, and feel to the touch, so it is used as an additive or main agent for various applications.
• the organopolysiloxane polymer and the crosslinked product have low tensile strength and hardness and cannot be used as a molded product.
• Tensile product is the product of tensile strength and tensile elongation at break and is used as an index of energy to break a material.
• the tensile product of the crosslinked organopolysiloxane is 20 to 200 without the filler, and the tensile strength is less than 2 MPa.
• acrylic resin has the advantages of high hardness, high tensile strength, transparency, gloss, and workability, and is used in applications such as paints, adhesives, and aquarium water tanks.
• the acrylic resin which is excellent in tensile strength, has a low tensile elongation at break of 2 to 7%, and therefore has a low tensile product of 100 to 500.
• the interpenetrating network polymer is also called an IPN resin and has a structure in which another resin chain passes through the crosslinked network of one resin. Due to this structure, even resins having poor compatibility can exist as a uniform polymer without being separated.
• interpenetrating network polymers are made by polymerizing a first polymer to create a first network and then a second polymer.
• the compatibility between the organopolysiloxane and the acrylic polymer is poor, and even if they are mixed, the two layers are immediately separated. For this reason, there are few reports of an interpenetrating network polymer composed of an organopolysiloxane and an acrylic polymer.
• Patent Document 1 discloses a resin composite material in which a resin and a molecular chain of a silane polymer such as silsesquioxane form an IPN structure.
• Preferred resins include polyolefin and polyamide. , Polystyrene, polycarbonate, polyurethane, ABS resin.
• 100 parts by mass of the above resin and 10-40 parts by mass of 3-glycidoxypropyltriethoxysilane or vinyltriethoxysilane are melt-kneaded in Laboplast mill. Then, after reacting the vinyl group or the glycidoxy group with the resin, a sheet is formed by pressing and immersed in warm water at 80° C.
• the condensation reaction of silane is required for a long time, and the condensation reaction with warm water has a different degree of progress of reaction between the outside and inside of the resin, so that the inside may not be sufficiently cured.
• the viscoelasticity and the coefficient of linear expansion are checked to confirm the IPN conversion, but the mechanical properties have not been measured.
• Patent Document 2 Japanese Patent No. 3993143 (Patent Document 2) relates to a method for producing a semi-IPN complex, in which a cross-linking agent containing a terminal silanol group-containing polysiloxane and a trialkoxysilane having an ammonium salt structure and a radically polymerizable monomer. It is proposed that the bodies are mixed and polymerized. This application is for paints that inhibit the adhesion of marine organisms, and the semi-IPN structure has biofouling repellent activity. Moreover, there is no description about the mechanical properties of the resin.
• Patent Document 3 discloses a hydrous polymer gel material for a medical material molded article having the properties of two kinds of polymers constituting a polymer gel having a network structure, which is a cellulose derivative.
• a polymer having reactivity with an isocyanate group such as, and a polymer copolymerizable with a (meth)acrylic group or a vinyl group are crosslinked with a (meth)acrylic acid derivative or a vinyl derivative having an isocyanate group. ..
• the highest tensile product in the examples is 550, which is not high.
• the present invention has been made in view of the above circumstances, and an interpenetrating network composed of a crosslinked organopolysiloxane and a (meth)acrylic polymer having both high tensile elongation at break of organopolysiloxane and high tensile strength of acrylic resin. It is an object to provide a polymer and a method for producing the polymer.
• the inventors of the present invention have made (A) a crosslinked organopolysiloxane to contain (b) a (meth) acrylic monomer and then polymerize a (meth) acrylic group.
• (B) (meth) acrylic polymer or (b) alkenyl group-containing organopolysiloxane and (a2) organohydrogen polysiloxane are added in a solution containing (meth) acrylic monomer.
• the interpenetrating network polymer composed of 90 to 30 parts by mass of the product and 10 to 70 parts by mass of the (B) (meth)acrylic polymer (however, the total of the components (A) and (B) is 100 parts by mass).
• the tensile product obtained by using a 2 mm thick sheet according to the evaluation method according to ISO37 is 1,000 or more, and the mechanical properties are significantly improved compared to conventional products. Therefore, the present invention has been completed.
• the present invention provides the following interpenetrating network polymer and a method for producing the same.
• the tensile product product of tensile strength (MPa) and tensile elongation at break (%) of a 2 mm-thick sheet containing no filler obtained by measurement according to ISO37 (JIS K 6251) is 1,000 or more.
• An interpenetrating network polymer characterized by the following. 2. 2.
• the interpenetrating network polymer according to 1 which has a tensile strength of 3 MPa or more and a tensile elongation at break of 300% or more obtained by a measurement of a 2 mm-thick sheet containing no filler according to ISO37. 3.
• the interpenetrating network polymer according to 1 or 2 wherein the (A) crosslinked organopolysiloxane is an addition reaction product of (a1) alkenyl group-containing organopolysiloxane and (a2) organohydrogenpolysiloxane.
• the (A) crosslinked organopolysiloxane contains (b) a (meth) acrylic monomer, and the (meth) acrylic group is polymerized to obtain a (B) (meth) acrylic polymer.
• Process for producing interpenetrating network polymer 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) a crosslinked organopolysiloxane, 5.
• the interpenetrating network polymer of the present invention is excellent in tensile strength and tensile elongation at break, has a tensile product of 1,000 or more, and has a high resistance which is not possible without the conventional incorporation of a large amount of filler. Have a stretch. For this reason, it becomes possible to make a molded body that is more robust than a (meth)acrylic resin that has not been available in the past, a sealant that is not easily broken, and is not brittle.
• the interpenetrating network polymer of the present invention comprises 90 to 30 parts by mass of (A) organopolysiloxane crosslinked product and 10 to 70 parts by mass of (B) (meth)acrylic polymer (provided that components (A) and (B) are The total is 100 parts by mass.).
• the mixing ratio of the (A) component and the (B) component is 90 to 30 parts by mass of the (A) component, 10 to 70 parts by mass of the (B) component, and preferably 80 to 50 parts by mass of the (A) component.
• the component (B) is 20 to 50 parts by mass, and the component (A)+(B) is 100 parts by mass.
• the component (A) is a crosslinked organopolysiloxane.
• Examples of the method for synthesizing the crosslinked organopolysiloxane product include condensation, peroxide crosslinking, UV crosslinking, and addition reaction. Among them, the addition reaction type having a short reaction time is preferable.
• the addition reaction type organopolysiloxane crosslinked product will be specifically described. After the components (a1), (a2) and (c) below are mixed to prepare an addition reaction type organopolysiloxane composition, the composition is prepared. Can be produced by heat curing.
• the component (a1) is an alkenyl group-containing organopolysiloxane and has a weight average molecular weight of 800 or more and 80,000 or less and a vinyl value of 0.003 mol/100 g or more and 0.7 mol/ which is represented by the following general formula (1). It is preferably 100 g or less of an organopolysiloxane having two or more alkenyl groups in the molecule.
• 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 is RSiO 3/2
• T vi is KSiO 3/2 and Q are SiO 4/2
• R is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms and having no aliphatic unsaturated bond
• E, g, and i cannot be 0 at the same time, 2 ⁇ e+g+i ⁇ 500, f is a positive number from 10 to 1,000, h is 0 or a positive number less than 20, and j is It is a positive number less than 0 or 10.
• each R is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms and having no aliphatic unsaturated bond, and R having 1 to 10 carbon atoms. Particularly, those having 1 to 8 carbon atoms are preferable.
• alkyl groups such as methyl group, ethyl group, propyl group, butyl group and octyl group, cycloalkyl groups such as cyclohexyl group, phenyl group and tolyl group.
• Groups such as aryl groups, benzyl groups, phenethyl groups, and other aralkyl groups, and the like.
• Halogen atom substitutions such as chloropropyl groups and trifluoropropyl groups in which some or all of these hydrogen atoms are replaced with halogen atoms, etc.
• An alkyl group is mentioned.
• R is preferably a methyl group or a phenyl group.
• the alkenyl group represented by —(CH 2 ) L —CH ⁇ CH 2 (L is a positive number of 0 or 6 or less) of K is specifically a vinyl group, an allyl group, a butenyl group, a propenyl group. , 5-hexenyl group, octenyl group and the like, among which vinyl group is preferable.
• D, e, g, and i in the formula (1) are each independently 0 or a positive number exceeding 0, d is preferably a positive number of 0 or 100 or less, and e is a positive number of 0 or 100 or less. Is preferred, g is preferably 0 or a positive number of 500 or less, and i is preferably 0 or a positive number of 100 or less. e, g, and i do not become 0 at the same time, and e+g+i is a positive number of 2 or more and 500 or less, preferably 2 or more and 200 or less.
• the number f of D (R 2 SiO 2/2 structure) units in the formula (1) is a positive number of 10 or more and 1,000 or less, preferably a positive number of 40 or more and 800 or less, and more preferably 100 or more. It is a positive number of 600 or less. If f is less than 10, tensile elongation at break may be too low. If f is more than 1,000, the hardness may be too low.
• h is 0 or a positive number of 20 or less, preferably 0 or 10 or less
• j is a positive number of 0 or 10 or less, preferably 0 or 5 or less.
• the vinyl value of the alkenyl group-containing organopolysiloxane represented by the formula (1) is 0.00105 mol/100 g or more and 0.7 mol/100 g or less, preferably 0.005 mol/100 g or more and 0.5 mol/100 g or less, and more preferably It is preferably 0.005 mol/100 g or more and 0.3 mol/100 g or less. If the vinyl value is less than 0.003 mol/100 g, the hardness may be too low. If the vinyl value is 0.7 mol/100 g or more, the tensile elongation at break may be too low.
• the weight average molecular weight of the alkenyl group-containing organopolysiloxane represented by the formula (1) is 800 or more and 80,000 or less, preferably 3,000 or more and 60,000 or less, and more preferably 5,000 or more and 40, It is 000 or less. If the weight average molecular weight is lower than 800, the tensile elongation at break may be too low. If it is higher than 80,000, the hardness may be too low. In the present invention, the weight average molecular weight is a value determined by 29 Si-NMR (hereinafter the same).
• Kinematic viscosity at 25 ° C. of the alkenyl group-containing organopolysiloxane represented by the formula (1) is preferably 7 ⁇ 30,000mm 2 / s, more preferably 100 ⁇ 3,000mm 2 / s.
• the kinematic viscosity is a value measured by an Ostwald viscometer (hereinafter the same).
• alkenyl group-containing organopolysiloxane represented by the formula (1) include both-end-alkenyl-group-containing siloxanes, side-chain alkenyl-group-containing siloxanes, one end and side-chain alkenyl-group-containing siloxanes, both ends and Examples thereof include a side chain alkenyl group-containing siloxane and a branched terminal alkenyl group-containing siloxane.
• More specific structural examples include 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.
• the component (a2) is an organohydrogenpolysiloxane having a kinematic viscosity at 25° C. of 2 mm 2 /s or more and 500 mm 2 /s or less and at least a hydrogen atom (SiH group) bonded to a silicon atom in one molecule. It is preferably an organohydrogenpolysiloxane having two.
• the crosslinked organopolysiloxane (A) is formed by the addition reaction between the SiH group of the organohydrogenpolysiloxane of the component (a2) and the alkenyl group of the alkenyl group-containing organopolysiloxane of the component (a1).
• the number of hydrogen atoms (SiH groups) bonded to a silicon atom in one molecule is preferably 2 to 100, more preferably 4 to 80.
• the content of SiH group in the component (a2) is preferably 0.0021 to 3.5 mol/100 g, more preferably 0.01 to 2.5 mol/100 g, and further preferably 0.02 to 2. It is 0 mol/100 g. If the SiH group content is too low, the curability may deteriorate, and if it is too high, the tensile elongation at break may be too low.
• the kinematic viscosity of the component (a2) at 25° C. is preferably 2 mm 2 /s or more and 500 mm 2 /s or less, more preferably 2 mm 2 /s or more and 300 mm 2 /s or less, and further preferably 5 mm 2 /s. It is s or more and 200 mm 2 /s or less. If the kinematic viscosity is less than 2 mm 2 /s, the tensile elongation at break may be too low. If it is higher than 500 mm 2 /s, the curing property may deteriorate. In the present invention, the kinematic viscosity can be measured with an Ostwald viscometer.
• the organohydrogenpolysiloxane of the component (a2) may contain a (meth)acrylic group, and when it contains a (meth)acrylic group, the (meth)acrylic group of the component (b) is It can be polymerized with a (meth)acrylic group in a (meth)acrylic monomer to form a polymer having a strong interpenetrating network structure.
• a (meth)acrylic group its content is preferably 0.016 to 1.6 mol/100 g, more preferably 0.02 to 1.0 mol/100 g. If the content of the (meth)acrylic group is too small, it may not react with the acrylic monomer and the mechanical strength may not change, and if it is too large, a uniform interpenetrating network structure may not be formed.
• organohydrogenpolysiloxane as the component (a2), those having a structure represented by the following general formula (2) are preferable.
• 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
• Q is SiO 4/2
• R is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms and having no aliphatic unsaturated bond.
• m, n, o and q are each independently 0 or a positive number exceeding 0, p is a positive number of 2 to 100, r is a positive number of 0 or 10 or less, and s is a positive number of 0 or 10 or less. Yes, n, p, and r do not become 0 at the same time, and 2 ⁇ n+p+r ⁇ 100.)
• each R is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms and having no aliphatic unsaturated bond, and is the same as R in the formula (1).
• Examples thereof include alkyl groups having 1 to 8 carbon atoms.
• M, n, o, and q in formula (2) are each independently 0 or a positive number exceeding 0, m is preferably a positive number of 0 or 10 or less, and n is a positive number of 0 or 10 or less. It is preferably a number, o is preferably a positive number of 0 or 100 or less, and q is preferably a positive number of 0 or 10 or less. Further, p is a positive number of 2 to 100, preferably 4 to 80, r is a positive number of 0 or 10 or less, preferably 0 or 5 or less, and s is 0 or 10 or less. Is a positive number, preferably 0 or a positive number of 5 or less. In addition, n+p+r is a positive number of 2 to 100, preferably 4 to 80.
• the weight average molecular weight of the organohydrogenpolysiloxane is preferably 194 to 10,000, more preferably 874 to 8,500. If the weight average molecular weight is too small, the tensile elongation at break may be too low, and if it is too large, the reactivity may be deteriorated and the curing property may be lowered.
• organohydrogenpolysiloxane of the component (a2) include hydrogen silyl group-containing siloxanes having both terminals, side chain hydrogen silyl group-containing siloxanes, one-terminal and side chain hydrogen silyl group-containing siloxanes, Examples include siloxanes containing hydrogen silyl groups at both ends and side chains.
• the blending amount of the component (a2) is such that the hydrogen atom (SiH group) bonded to a silicon atom is in the range of 0.5 to 5 mol with respect to 1 mol of the alkenyl group of the component (a1). 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 when considering the amount of SiH functional groups. If the amount of the component (a2) is too large, the crosslink density is low and the network structure of the crosslink is large in some cases, resulting in a weak strength structure.
• the component (c) is a platinum group metal-based catalyst, and a known catalyst used as an addition reaction catalyst can be used.
• platinum group metal-based catalysts include platinum-based, palladium-based, rhodium-based, and ruthenium-based catalysts, and of these, platinum-based catalysts are particularly preferably used.
• platinum-based catalysts include chloroplatinic acid, alcoholic or aldehyde solutions of chloroplatinic acid, complexes of chloroplatinic acid with various olefins or vinylsiloxanes, complexes of platinum with various olefins or vinylsiloxanes, and the like. ..
• the addition amount of the (c) platinum group metal-based catalyst 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 the later-described Platinum group metal mass (platinum group metal mass/composition total mass ((a1)+(a2)+(b)+(c)+(d)+(e) with respect to the total mass of components (d) and (e)) )))) is preferably 1 to 200 ppm, particularly preferably 5 to 100 ppm.
• the addition reaction control agent of the component (d) is a component which is added as necessary, and controls the catalytic activity of the platinum group metal-based catalyst, and is composed of various organic nitrogen compounds, organic phosphorus compounds, acetylene compounds, oxime compounds. , Organic chloro compounds and the like.
• Acetylene-based alcohols such as oat and phenylbutynol
• acetylene-based compounds such as 3-methyl-3--1-pentene-1-yne and 3,5-dimethyl-1-hexyne-3-yne
• organic nitrogen compounds such as benzotriazole and other organic phosphorus compounds, oxime compounds, Examples thereof include maleic acid compounds and organic chromium compounds.
• the addition amount of the addition reaction control agent (d) should be 0.01 to 100 parts by weight in total of the components (A) and (B), as long as good treatment bath stability can be obtained. It is 5 parts by mass, preferably 0.1 to 3 parts by mass.
• the addition reaction type organopolysiloxane crosslinked product is an addition reaction type organopolysiloxane obtained by mixing the above-mentioned component (a1), component (a2), component (c) and, if necessary, component (d). After the composition is prepared, it can be produced by heat-curing the composition at 20 to 200° C., especially 40 to 150° C. for 10 seconds to 2 hours, especially 1 minute to 1.5 hours.
• the addition reaction type organopolysiloxane crosslinked product preferably has a reaction rate of 90% or more between the component (a1) and the component (a2), and is 93 to 100%. More preferably.
• the reaction rate can be calculated by measuring the hydrogen gas generation amount. How to obtain hydrogen gas generation rate; 5 to 10 g of the crosslinked organopolysiloxane and the organopolysiloxane composition are placed in a Meyer, diluted with about 10 g of n-butanol, and set in a gas buret. The solution is stirred with a stir bar. 20 ml of 20 mass% NaOH aqueous solution is put into the dropping funnel, and dropped into the Mayer.
• Hydrogen gas generation rate (ml/g) [value of scaled hydrogen gas generation rate ml/g] x 273 / (temperature (°C) + 273) x atmospheric pressure (hPa) / 1013 (hPa) How to obtain the reaction rate; It is calculated from the above hydrogen gas generation amount by the following calculation formula.
• Reaction rate (%) ⁇ 1-(hydrogen gas generation amount of crosslinked organopolysiloxane (composition after reaction) (ml/g)/hydrogen gas generation amount of organopolysiloxane composition (composition before reaction) (ml) /G)) ⁇ 100
• the component (B) is a (meth)acrylic polymer, and is obtained by polymerizing the (meth)acrylic monomer (b).
• the (meth)acrylic monomer includes a compound having one (meth)acrylic group and two or more compounds.
• the compound containing a (meth)acrylic group preferably has a weight average molecular weight of 72 to 1,000 and is represented by the following formula (3).
• (CH 2 CR 1 COY) a Z (3)
• 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)
• R is a carbon atom having no aliphatic unsaturated bond. It is an unsubstituted or substituted monovalent hydrocarbon group of the number 1 to 12.
• a is an integer of 1 to 4
• Z is a mono to tetravalent organic group.
• Y is an oxygen atom or NR 2 (R 2 is a hydrogen atom or R).
• R is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, which does not have an aliphatic unsaturated bond, and is the same as that exemplified as R in the above formula (1). It can be illustrated.
• a is an integer of 1 to 4, preferably an integer of 1 to 3.
• Z is a monovalent to tetravalent organic group, and when a is 4, Z is preferably a carbon atom. When a is 3, Z is preferably a trivalent group having 2 to 12 carbon atoms such as (—CH 2 ) 3 CR (R is the same as above). 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 the number of carbon atoms. It is preferably 4 to 20 polyoxyalkylene groups, and a hydroxyl group, an epoxy group, or an isocyanate group may be partially present.
• 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, and which may be fluorine- or hydroxy-substituted. It is preferably a monovalent hydrocarbon group having a number of 1 to 30, preferably 1 to 24. )
• the alkylene group having 1 to 30 carbon atoms is preferably an alkylene group having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and specific examples thereof include methylene, ethylene and 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.
• 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 can be mentioned.
• Examples of the oxyalkylene group include an oxyethylene group, oxypropylene group and oxybutylene group, and examples of the polyoxyalkylene group include a polyoxyethylene group, a polyoxypropylene group and a polyoxybutylene group. Further, a hydroxyl group, an epoxy group, or an isocyanate group may exist in a part of hydrogen atoms of these groups.
• Examples of the monovalent hydrocarbon group having 1 to 30 carbon atoms, preferably 1 to 24 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group.
• specific examples of the compound containing one (meth)acrylic group include the following compounds. 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, 4-hydroxybutyl acrylate, acrylic acid, butyl acrylate, methyl acrylate, ethyl acrylate, tertiary butyl acrylate, isobutyl acrylate, methacrylic acid, isodecyl acrylate, stearyl Acrylate, behenyl acrylate, lauryl acrylate, ethyl diglycol acrylate, propylheptyl acrylate, dicyclopentanyl acrylate, isobornyl acrylate, cyclohexyl methacrylate, tertiary butyl methacrylate, ureido methacrylate, lauryl methacrylate, stearyl methacrylate, be
• the compound containing two or more (meth)acrylic groups in the (b) (meth)acrylic monomer may be mentioned as specific examples.
• isobornyl acrylate is particularly preferable because the compatibility with the crosslinked organopolysiloxane is slightly better than other acrylic monomers.
• the polymerization of (b) (meth) acrylic monomer can be carried out using (e) radical initiator.
• the polymerization of the (b) (meth) acrylic monomer may be carried out by adding the component (b) to the component (A) or by mixing the components (a1), (a2) and (b) in advance, and ), it is preferable to polymerize the component (b) after the addition reaction of the component (a2).
• the radical initiator (e) is a component that is added to polymerize the (meth)acrylic monomer, and is a compound that decomposes by heat or light irradiation to generate radicals.
• the (meth)acrylic group is polymerized by the generated radicals.
• the radical initiator known ones can be used, for example, organic peroxide, dihalogen, azo compound, redox catalyst, triethylborane, diethylzinc, alkylphenone photopolymerization initiator, acylphosphine oxide photopolymerization initiator.
• the compounding amount of the (e) radical initiator is generally 0.01 to 100 parts by mass with respect to 100 parts by mass of the total of the components (A) and (b) (or the total of (a1), (a2) and (b)).
• the amount is preferably 25 parts by mass, more preferably 0.1 to 15 parts by mass, still more preferably 1 to 10 parts by mass. If the amount of the component (e) is too small, the polymerization of the component (b) may not proceed, and if it is too large, the termination reaction may easily occur and the degree of polymerization may be low.
• organic solvent an organic solvent soluble in organopolysiloxane such as toluene, hexane, xylene or methyl ethyl ketone (not including a siloxane solvent), a low viscosity cyclic siloxane such as octamethyl tetrasiloxane or decamethyl pentasiloxane, M 2 D n (M and D are the same as above.
• organopolysiloxane such as toluene, hexane, xylene or methyl ethyl ketone (not including a siloxane solvent)
• a low viscosity cyclic siloxane such as octamethyl tetrasiloxane or decamethyl pentasiloxane
• M 2 D n M and D are the same as above.
• n is a positive number of 0 or less than 200, preferably a positive number of 1 to 50), etc.
• M 2+m D n T m M , D and T are the same as above, n is a positive number of 0 or less than 200, 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.
• organopolysiloxane siloxane solvent
• siloxane solvent such as the branched-chain siloxane.
• the amount of the solvent to be used is 0 of the total (or the total of (a1), (a2) and (b) components) mass of the crosslinked organopolysiloxane of the (A) component and the (meth)acrylic monomer of the (b) component. It is preferably ⁇ 50 times, and particularly preferably 8 to 30 times.
• high molecular weight hydrocarbons for the purpose of giving slipperiness, high molecular weight linear organopolysiloxanes, silicone resins having aryl groups, silicone resins, silica, silicone powders, fillers such as talc and mica to increase mechanical strength, Acrylic silicone or the like can be added as a compatibilizer, if necessary.
• the addition amount of the optional component can be a normal amount within a range that does not impair the effects of the present invention.
• the interpenetrating network polymer of the present invention is prepared, for example, by mixing the above-mentioned component (A) with the component (b) and the component (e), and adding the (meth)acrylic group of the component (b) and the component (A).
• the interpenetrating network polymer can be prepared by polymerizing these (meth)acrylic groups to obtain the component (B), but the above (a1), ( a2) and (b) components, further (c) and (e) components, and optionally (d) component and other components are mixed in advance to prepare a composition for an interpenetrating network polymer, and the composition is prepared.
• the components (a1) and (a2) therein are subjected to an addition reaction to obtain the component (A), and then the component (b) has a (meth)acrylic group and the component (A) has a (meth)acrylic group.
• the component (B) it is preferable to prepare the interpenetrating network polymer by polymerizing these (meth)acrylic groups to obtain the component (B).
• the above-mentioned components (a1), (a2), (b), (d), (e) and optional components are uniformly mixed in advance and then the component (c) is added.
• Each component may be used alone or in combination of two or more.
• the mixing ratio of these components (a1) to (a2) and (b) is The total mass ratio of components (a1) and (a2):component (b) is preferably 90:10 to 30:70, and more preferably 80:20 to 50:50.
• the kinematic viscosity at 25° C. of the obtained composition for interpenetrating network polymer is preferably 3,000 mm 2 /s or less, more preferably 100 to 2,000 mm 2 /s, and 150 to 1 , 500 mm 2 /s is more preferable. If the kinematic viscosity is too low, the tensile elongation at break may be too low. If it is too high, the curability may deteriorate.
• the addition reaction conditions of the components (a1) and (a2) in the above preparation method are preferably 20 to 180° C., particularly 40 to 150° C., and 10 minutes to 3 hours, particularly 30 minutes to 2 hours.
• the polymerization of the (meth)acrylic group of the component (b) or the (meth)acrylic group in the component (A) can be carried out by UV irradiation, and the polymerization conditions are, specifically, 200 Irradiate with UV light having a wavelength of up to 500 nm for 1 to 60 seconds.
• the integrated light amount is preferably 2,000 to 10,000 mJ/cm 2 , and more preferably 3,000 to 8,000 mJ/cm 2 .
• a tensile product (tensile strength (MPa) and tensile rupture) of a 2 mm-thick sheet containing no filler obtained by measurement according to ISO37 (JIS K6251)
• the product of elongation (%) is 1,000 or more, preferably 1,000 to 10,000, and more preferably 1,000 to 5,000.
• the tensile product is less than 1,000, the polymer becomes brittle.
• the reaction rate of the components (a1) and (a2) is 90% or more, and for the acrylic polymerization, the non-volatile content of the interpenetrating network polymer is preferably 90% or more.
• the nonvolatile content of the interpenetrating network polymer is preferably 85% or more, more preferably 90% or more.
• the nonvolatile content can be measured by extracting the obtained interpenetrating network polymer with toluene and drying it, then measuring the mass of the residual polymer, and measuring the difference from the mass of the polymer before extraction with toluene.
• 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 interpenetrating network polymer of the present invention is excellent in tensile strength and tensile elongation at break, and has a tensile product of 1,000 or more, which is a high tensile product that could not be achieved without a conventional large amount of filler. Therefore, it becomes possible to manufacture a molded body that is more robust than a (meth)acrylic resin, which is not available in the past, and a sealant that is hard to break and is not brittle. Specifically, it is useful as a housing for electronic parts, remote controllers, personal computers, mobile phones, televisions, and the like.
• the reaction rate was calculated by measuring the hydrogen gas generation amount, the hydrogen gas generation amount was measured by the method shown below, and the nonvolatile content was 100 times the polymer mass. It can be determined from the difference between the polymer mass obtained by impregnating the polymer in toluene of a corresponding mass for 1 day, removing the toluene, and drying the swollen polymer at 100° C. for 1 hour and the mass of the polymer before impregnation with toluene. it can.
• the weight average molecular weight of the organopolysiloxanes listed below as starting materials was determined by 29 Si-NMR.
• Methyl vinyl polysiloxane (1) 87.5 parts by mass as the component (a1), methyl hydrogen polysiloxane (2) 12.5 parts by mass as the component (a2), and isobornyl acrylate (4) 38 as the component (b).
• composition for an interpenetrating network polymer having a ratio of SiH groups in the above was prepared. After the above composition was put into a fluorine-coated mold frame having a depth of 2 mm and an area of 15 cm ⁇ 20 cm, a fluorine-coated metal plate was placed and sandwiched, and the mixture was heated at 50° C. for 1 hour to obtain an organopolysiloxane.
• the component (a1) and the component (a2) were crosslinked (reaction rate 94%).
• 4,000 mJ/cm 2 of the crosslinked organopolysiloxane containing the component (b) was irradiated with a metal halide lamp (wavelength: 200 to 500 nm, particularly a large output of 300 to 450 nm) in a nitrogen atmosphere using a UV irradiation device.
• the acrylic group in the composition (in the component (b)) was polymerized by irradiating with UV with the integrated light amount of (3) to synthesize an interpenetrating network polymer (90% non-volatile content of the interpenetrating network polymer).
• Methyl vinyl polysiloxane (1) 86.1 parts by mass as the component (a1), acryl group-containing methyl hydrogen polysiloxane (3) 13.9 parts by mass as the component (a2), and isobornyl acrylate (as the component (b) ( 4) 43 parts by mass, (d) 0.15 parts by mass of 1,1-dimethylpropynyloxytrimethylsilane as an addition reaction control agent component, and (e) 4 parts by mass of Irgacure 1173 as a radical initiator were added until uniform.
• Example 2 The production was carried out under the same conditions as in Example 1 (reaction rate of the component (a1) and the component (a2) was 96%), and an interpenetrating network polymer was synthesized (nonvolatile content of the interpenetrating network polymer was 92%).
• Methyl vinyl polysiloxane (1) 86.1 parts by mass as the component (a1), acryl group-containing methyl hydrogen polysiloxane (3) 13.9 parts by mass as the component (a2), and isobornyl acrylate (as the component (b) ( 4) 78.9 parts by mass, (d) 0.15 parts by mass of 1,1-dimethylpropynyloxytrimethylsilane as an addition reaction control agent component, and (e) 4 parts by mass of Irgacure 1173 as a radical initiator were added to obtain a uniform mixture.
• Isobornyl acrylate (4) Compound represented by the following formula (4) (molecular weight 208.3, specific gravity 0.983 g/ml)

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