Resin composition containing silicone-vinyl acetate copolymer resin and method for producing the same

Abstract

SOLUTION: The present invention provides a silicone / vinyl acetate copolymer resin that is a resin composition including (A) an organopolysiloxane unit derived from an organopolysiloxane represented by a specified general formula, (B) a copolymer resin with a vinyl acetate unit, and (C) a water-soluble polymer, wherein the weight ratio of the organopolysiloxane unit (A) to the vinyl acetate unit (B) is (A): (B)=10:90-95:5, and the mass ratio of the vinyl acetate unit (B) to the water-soluble polymer (C) is 100:5-50.EFFECT: The resin composition according to the present invention has sliding properties, to-substrate adhessibility, and organic solvent solubility, and is suitably used for coating agents for various substrates, adhesives, exterior and interior coating materials for structural and building materials, cosmetics, and the like.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a resin composition containing a resin obtained by copolymerizing organopolysiloxane with vinyl acetate, and a method for producing the same. More specifically, it relates to a silicone-vinyl acetate copolymer resin having sliding properties, substrate adhesion, solvent resistance, and scratch resistance, and a method for producing the same. [Background technology]

[0002] Silicone resins have traditionally been known as resins that can impart sliding properties to substrates. However, when silicone resins are used alone, there have been problems such as poor adhesion to the substrate.

[0003] Therefore, methods are used in which silicone resins are copolymerized with other monomers such as acrylic or urethane. For example, copolymers such as acrylic silicone copolymers and urethane silicone copolymers can impart the advantages of silicone resins, such as weather resistance, heat resistance, cold resistance, water repellency, gas permeability, and sliding properties, to ordinary acrylic or urethane emulsions. For example, Patent Document 1 (Japanese Patent Application Publication No. 2020-90563) discloses a silicone acrylic bluff copolymer resin that imparts sliding properties and a method for producing the same.

[0004] On the other hand, vinyl acetate resin has been conventionally used in emulsion adhesives, photosensitive materials for screen printing, laundry starch, chewing gum bases, emulsifiers, and cosmetic substrates, and is known as a resin with good adhesion.

[0005] An example of a resin obtained by copolymerizing vinyl acetate resin with another monomer is ethylene vinyl acetate copolymer, which is obtained by copolymerizing ethylene. This copolymer is a synthetic resin that possesses adhesiveness and flexibility due to the vinyl acetate unit, and is used in coating materials for paper containers such as food packaging paper and paper cups, adhesives for cloth and paper labels, emulsion adhesives, chewing gum bases, artificial turf, sandal soles, bath mats, bathroom cleaning boots, kickboards, jump ropes, and more.

[0006] Silicone resin and vinyl acetate resin are resins with opposite properties. However, as the inventors previously disclosed in Japanese Patent Application Laid-Open No. 2022-131528, they have succeeded in developing a silicone-vinyl acetate copolymer resin that combines the properties of silicone resin and vinyl acetate resin.

[0007] However, the silicone-vinyl acetate copolymer resin has drawbacks such as poor solvent resistance and scratch resistance, leaving room for improvement.

Prior Art Documents

Patent Documents

[0008]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0009] The present invention has been made in view of the above circumstances, and an object thereof is to provide a resin composition containing a silicone-vinyl acetate copolymer resin having slidability, substrate adhesion, solvent resistance, and scratch resistance, and a method for producing the same.

Means for Solving the Problems

[0010] As a result of intensive studies to achieve the above object, the present inventors have found that a resin composition obtained by incorporating (C) a water-soluble polymer into a copolymer resin of (A) an organopolysiloxane unit and (B) a vinyl acetate unit has slidability, substrate adhesion, solvent resistance, and scratch resistance, and have thus completed the present invention.

[0011] Therefore, the present invention provides a resin composition containing the following silicone-vinyl acetate copolymer resin, a method for producing the same, and a dispersion liquid. 1. A resin composition comprising a copolymer resin of an organopolysiloxane unit derived from an organopolysiloxane represented by the following general formula (1) and a vinyl acetate unit, and polyvinyl alcohol, wherein the mass ratio of the above (A) organopolysiloxane unit to the above (B) vinyl acetate unit is (A):(B)=10:90 to 95:5, and the mass ratio of the above (B) vinyl acetate unit to the above (C) polyvinyl alcohol is 100:15 to 50.

Chemical formula

Chem.

[0012] The resin composition containing the silicone-vinyl acetate copolymer resin of the present invention has sliding properties, substrate adhesion, solvent resistance, and scratch resistance. For this reason, the resin composition of the present invention is suitably used as a coating agent for various substrates, an adhesive, an exterior and interior paint for structures and building materials, and a cosmetic. [Modes for carrying out the invention]

[0013] The present invention is a resin composition comprising (A) an organopolysiloxane unit and (B) a vinyl acetate unit copolymer resin containing (C) a water-soluble polymer.

[0014] In the present invention, (A) organopolysiloxane unit is derived from the organopolysiloxane represented by the following general formula (1). [ka] (In the formula, R 1 R is a monovalent hydrocarbon group having 1 to 20 carbon atoms, either identical or different substituted or unsubstituted groups. 2is a mercapto group, an acryloxy group, or a methacryloxy group-substituted alkyl group having 1 to 6 carbon atoms, or a vinyl group. X is the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a hydroxyl group, and Y is X or -[O-Si(X)2] d -X represents the same or different groups, where at least two of X and Y are hydroxyl groups. Z is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydroxyl group. a is a positive number from 0 to 1,000, b is a positive number from 100 to 10,000, c is a positive number from 1 to 10, and d is a positive number from 1 to 1,000.

[0015] Here, R 1 These are identical or different substituted or unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, specifically alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, and octadecyl groups; cycloalkyl groups such as cyclopentyl, cyclohexyl, and cycloheptyl groups; alkenyl groups such as vinyl and allyl groups; aryl groups such as phenyl, tolyl, and naphthyl groups; and vinyl compounds. Examples include alkenylaryl groups such as phenyl groups, aralkyl groups such as benzyl groups, phenylethyl groups, and phenylpropyl groups, alkenylaralkyl groups such as vinylbenzyl groups and vinylphenylpropyl groups, and groups in which some or all of the hydrogen atoms of these groups are substituted with halogen atoms such as fluorine, bromine, and chlorine, acryloxy groups, methacryloxy groups, carboxyl groups, alkoxy groups, alkenyloxy groups, amino groups, alkyl or alkoxy or (meth)acryloxy-substituted amino groups. 1 Preferably, it is a methyl group.

[0016] R 2 This is a C1-C6 alkyl group substituted with a mercapto group, an acryloxy group, or a methacryloxy group, or a vinyl group. Specifically, mercaptopropyl group, acryloxypropyl group, methacryloxypropyl group, vinyl group, etc., are preferred.

[0017] X is the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a hydroxyl group, and as an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, R 1 Examples similar to those exemplified above can be given, and specific examples of alkoxy groups having 1 to 20 carbon atoms include methoxy, ethoxy, propoxy, butoxy, hexyloxy, heptyloxy, octyloxy, decyloxy, and tetradecyloxy groups. X is preferably a hydroxyl, methyl, butyl, or phenyl group.

[0018] Y is X or -[O-Si(X)2] d -X represents the same or different base.

[0019] Z is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydroxyl group, preferably a hydroxyl group or a methyl group.

[0020] If a is greater than 1,000, the strength of the coating obtained when a resin composition containing component (A) is used as a coating film will be insufficient, so it is set to a number between 0 and 1,000, preferably between 0 and 200. If b is less than 100, the flexibility of the coating will be poor, and if it is greater than 10,000, its tear strength will decrease, so it is set to a positive number between 100 and 10,000, preferably between 1,000 and 5,000. c is a positive number between 1 and 10, and if it exceeds 10, there is a problem that the sliding effect cannot be achieved.

[0021] d is a positive number between 1 and 1,000, preferably between 1 and 200. Furthermore, from the standpoint of crosslinking, it is preferable to use a molecule that has at least two, preferably two to four, hydroxyl groups in one molecule, formed at both ends.

[0022] Such organopolysiloxanes represented by the above general formula (1) are preferably used in emulsion form and may be commercially available or synthesized. When synthesized, known emulsion polymerization methods can be used, and for example, a cyclic organosiloxane or α,ω-dihydroxysiloxane oligomer, α,ω-dialkoxysiloxane oligomer, alkoxysilane, etc., which may have a fluorine atom, a (meth)acryloxy group, a carboxyl group, a hydroxyl group, or an amino group, can be easily synthesized by emulsifying and dispersing a silane coupling agent represented by the following general formula (2) in water using an anionic surfactant, and then adding a catalyst such as an acid as needed to carry out a polymerization reaction. R 3 (4-e-f) R 4 f Si(OR 5 ) e (2) (In the formula, R 3 R represents a monovalent organic group having a polymerizable double bond, particularly an alkyl group having 1 to 6 carbon atoms substituted with an acryloxy group or a methacryloxy group. 4 R is an alkyl group having 1 to 4 carbon atoms. 5 is an alkyl group having 1 to 4 carbon atoms, e is 2 or 3, f is 0 or 1, and e+f is 2 or 3. be.)

[0023] The above cyclic organosiloxanes include hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), 1,1-diethylhexamethylcyclotetrasiloxane, phenylheptamethylcyclotetrasiloxane, 1,1-diphenylhexamethylcyclotetrasiloxane, 1,3,5,7-tetravinyltetramethylcyclotetrasiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7-tetracyclohexyltetramethylcyclotetrasiloxane, tris(3,3,3-trifluoropropyl)trimethylcyclotrisiloxane, and 1,3,5,7-tetra(3-methacryloxypropyl)tetramethyl Examples include clotetrasiloxane, 1,3,5,7-tetra(3-acryloxypropyl)tetramethylcyclotetrasiloxane, 1,3,5,7-tetra(3-carboxypropyl)tetramethylcyclotetrasiloxane, 1,3,5,7-tetra(3-vinyloxypropyl)tetramethylcyclotetrasiloxane, 1,3,5,7-tetra(p-vinylphenyl)tetramethylcyclotetrasiloxane, 1,3,5,7-tetra[3-(p-vinylphenyl)propyl]tetramethylcyclotetrasiloxane, 1,3,5,7-tetra(N-acryloyl-N-methyl-3-aminopropyl)tetramethylcyclotetrasiloxane, and 1,3,5,7-tetra(N,N-bis(lauroyl)-3-aminopropyl)tetramethylcyclotetrasiloxane. Preferably, octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane are used.

[0024] Silane coupling agents include, specifically, vinylsilanes such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane, vinylmethyldimethoxysilane, and vinylmethyldiethoxysilane; γ-(meth)acryloxypropyltrimethoxysilane, γ-(meth)acryloxypropyltriethoxysilane, γ-(meth)acryloxypropyltripropoxysilane, γ-(meth)acryloxypropyltriisopropoxysilane, and γ-(meth)acryloxypropyltriisopropoxysilane. Examples include acrylic silanes such as roxypropyltributoxysilane, γ-(meth)acryloxypropylmethyldimethoxysilane, γ-(meth)acryloxypropylmethyldiethoxysilane, γ-(meth)acryloxypropylmethyldipropoxysilane, γ-(meth)acryloxypropylmethyldiisopropoxysilane, and γ-(meth)acryloxypropylmethyldibutoxysilane; and mercaptosilanes such as γ-mercaptopropylmethyldimethoxysilane and γ-mercaptopropyltrimethoxysilane. Alternatively, oligomers obtained by condensation polymerization of these may be more preferable as they suppress the generation of alcohols. Here, (meth)acryloxy refers to acryloxy or methacryloxy. These silane coupling agents are preferably used in amounts of 0.01 to 20 parts by mass, and more preferably 0.01 to 5 parts by mass, per 100 parts by mass of cyclic organosiloxane.

[0025] By copolymerizing the silane coupling agent, an organopolysiloxane having c in the following formula is obtained, and the effect of grafting (B-1) vinyl acetate is obtained. [ka]

[0026] For polymerization, any known polymerization catalyst may be used. Among these, strong acids are preferred, with hydrochloric acid, sulfuric acid, dodecylbenzenesulfonic acid, citric acid, lactic acid, and ascorbic acid being examples. Dodecylbenzenesulfonic acid, which has surfactant properties, is preferred.

[0027] The amount of acid catalyst used is preferably 0.01 to 10 parts by mass, and more preferably 0.2 to 2 parts by mass, per 100 parts by mass of cyclic organosiloxane.

[0028] Furthermore, as surfactants used in polymerization, anionic surfactants such as sodium lauryl sulfate, sodium laureth sulfate, N-acyl amino acid salts, N-acyl taurate salts, aliphatic soaps, and alkyl phosphates are used, but those that are easily soluble in water and do not have polyethylene oxide chains are preferred. More preferably are N-acyl amino acid salts, N-acyl taurate salts, aliphatic soaps, and alkyl phosphates, and particularly preferably sodium lauroyl methyl taurate, sodium myristoyl methyl taurate, and sodium lauryl sulfate.

[0029] The amount of anionic surfactant used is preferably 0.1 to 20 parts by mass, and more preferably 0.5 to 10 parts by mass, per 100 parts by mass of cyclic organosiloxane.

[0030] The polymerization temperature is preferably 50 to 75°C, and the polymerization time is preferably 10 hours or more, and more preferably 15 hours or more. Furthermore, it is particularly preferable to mature the product at 5 to 30°C for 10 hours or more after polymerization.

[0031] The weight-average molecular weight (Mw) of the organopolysiloxane (A) obtained in this way, as determined by viscosity measurement, is 10,000 to 1,000,000, preferably 100,000 to 500,000. If it is less than 10,000, there is a problem in that the sliding effect cannot be achieved.

[0032] Here, the weight-average molecular weight (Mw) of organopolysiloxane, determined by viscosity measurement, can be calculated from the specific viscosity ηsp (25°C) of a toluene solution of organopolysiloxane at a concentration of 1 g / 100 ml. ηsp = (η / η0) - 1 (η0: viscosity of toluene, η: viscosity of the solution) ηsp = [η] + 0.3[η] 2 [η] = 2.15 × 10 -4 M 0.65 Specifically, 20g of emulsion is mixed with 20g of IPA (isopropyl alcohol), the emulsion is broken down, the IPA is discarded, and the remaining rubbery organopolysiloxane is dried overnight at 60°C. This is then prepared as a toluene solution of organopolysiloxane at a concentration of 1g / 100ml, and the viscosity is measured at 25°C using an Ubbelohde viscometer. The molecular weight can be determined by substituting the viscosity into the above formula (References: Nakamuta, Nichika, 77 858

[1956] , Doklady Akad. Nauk. USSR 89 65

[1953] ).

[0033] The silicone-vinyl acetate copolymer resin of the present invention can be obtained by adding (C) a water-soluble polymer when emulsion graft polymerization of (B) vinyl acetate to (A-1) organopolysiloxane obtained as described above.

[0034] The mass ratio of the organopolysiloxane of formula (1) to vinyl acetate during graft polymerization (the mass ratio of the organopolysiloxane of formula (1) to vinyl acetate units) is 10:90 to 95:5, preferably 20:80 to 85:15. If the proportion of the polysiloxane component of formula (1) is less than 10, there is a problem in that the sliding effect cannot be achieved.

[0035] (C) Examples of water-soluble polymers include natural polymers such as proteins, starches, gelatin, and casein, modified natural polymers such as dextrin, methylcellulose, ethylcellulose, hydroxyethylcellulose, and carboxymethylcellulose, and synthetic polymers such as polyvinyl alcohol-based polymers, polyacrylic acid-based polymers, sodium polyacrylate-based polymers, polyvinylpyrrolidone-based polymers, polyacrylamide-based polymers, polyvinylamide-based polymers, polyamine-based polymers, and polyethylene oxide-based polymers. Preferably, the polymer is a polyvinyl alcohol-based polymer with surfactant properties.

[0036] The content of (C) water-soluble polymer in the silicone-vinyl acetate copolymer resin of the present invention is prepared so that the mass ratio of (B) vinyl acetate units to (C) water-soluble polymer is 100:5 to 50. Therefore, the amount of (C) water-soluble polymer used during emulsion graft polymerization is preferably adjusted so that the amount of (C) water-soluble polymer is 5 to 50 parts by mass in solid content per 100 parts by mass of (B-1) vinyl acetate used, and more preferably 10 to 40 parts by mass. If the amount of (C) component is less than 5 parts by mass, the solvent resistance effect cannot be exhibited, and if it exceeds 50 parts by mass, the sliding effect cannot be exhibited.

[0037] (C) The water-soluble polymer can be added at any time before, during, or after emulsion graft polymerization of (B-1) vinyl acetate to (A-1) organopolysiloxane. For example, (C) the water-soluble polymer may be added to (A-1) organopolysiloxane before (B-1) vinyl acetate is added and polymerization may be started, or (C) the water-soluble polymer may be added after polymerization of (A-1) organopolysiloxane and (B-1) vinyl acetate has started. When (C) the water-soluble polymer is added after polymerization has started, it is preferable to add (C) the water-soluble polymer when the polymerization rate of (A-1) and (B-1) is between 0.1% and 80%, and more preferably between 1% and 60%.

[0038] Radical initiators used when emulsifying and graft polymerizing (A-1) organopolysiloxane with (B-1) vinyl acetate include persulfates such as potassium persulfate and ammonium persulfate, hydrogen persulfate solution, t-butyl hydroperoxide, and hydrogen peroxide. If necessary, redox systems using reducing agents such as sodium acidic sulfite, rongalit, L-ascorbic acid, tartaric acid, sugars, and amines can also be used. The amount of the above radical initiator used is preferably 0.1 to 5 parts by mass, and more preferably 0.5 to 3 parts by mass, per 100 parts by mass of (B-1) vinyl acetate.

[0039] Graft polymerization is sufficiently possible due to the surfactant activity of the surfactant already contained in the organopolysiloxane emulsion and the water-soluble polymer (C). However, to improve stability, anionic surfactants such as sodium lauryl sulfate, sodium laureth sulfate, N-acyl amino acid salts, N-acyl taurine salts, aliphatic soaps, and alkyl phosphates can be added. Nonionic emulsifiers such as polyoxyethylene lauryl ether and polyoxyethylene tridecyl ether can also be added. When adding surfactants, the amount used is preferably 0.1 to 5 parts by mass per 100 parts by mass of (B-1) vinyl acetate.

[0040] The graft polymerization temperature of component (B) relative to component (A) is preferably 25 to 85°C, more preferably 75 to 85°C. The polymerization time is preferably 2 to 8 hours, more preferably 3 to 6 hours.

[0041] Furthermore, chain transfer agents can be added to adjust the molecular weight and grafting rate of the graft polymer. Examples include halogenated hydrocarbons such as chloroform and carbon tetrachloride; and mercaptans such as n-dodecyl mercaptan, tert-dodecyl mercaptan, and n-octyl mercaptan.

[0042] The resin composition containing the silicone-vinyl acetate copolymer resin obtained in this way is a polymer in which vinyl acetate is randomly grafted. The resulting resin composition is in a form in which a water-soluble polymer is dispersed around the silicone-vinyl acetate copolymer resin.

[0043] Furthermore, the resin composition containing the silicone-vinyl acetate copolymer resin obtained above preferably has a solid content of 25 to 40% by mass of the emulsion. The viscosity of this emulsion (at 25°C) is preferably 1 to 500 mPa·s, and more preferably 1 to 200 mPa·s. The viscosity can be measured using a rotational viscometer. The average particle size is preferably 0.1 μm (100 nm) to 0.5 μm (500 nm). The average particle size can be measured using a laser diffraction / scattering particle size distribution analyzer.

[0044] Furthermore, it is preferable that the total content of (A) a copolymer resin of organopolysiloxane units and (B) vinyl acetate units and (C) a water-soluble polymer in 100% by mass of the above emulsion (solid content) is preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more.

[0045] The resin composition containing the silicone-vinyl acetate copolymer resin of the present invention can also be granulated and powdered by the following methods. These include cryopreservation, spray drying, and airflow drying, and cryopreservation is preferred from the viewpoint of productivity. The above cryopreservation is carried out by known cryopreservation methods. Specifically, the resin is frozen by immersion in liquid nitrogen, and the frozen resin is put into a cryopreservation pulverizer and pulverized into a powder. Known cryopreservation pulverizers can be used. The average particle size of the resulting powder particles should be as small as possible, preferably 50 μm or less, and more preferably 1 to 30 μm. The particle size of the emulsion and powder can be measured as the cumulative mass average value D50 using a laser diffraction particle size analyzer.

[0046] The resin composition containing the silicone-vinyl acetate copolymer resin of the present invention can be used as a coating agent for various substrates such as synthetic resins, metals, glass, ceramics, gypsum, paper, wood, leather, lightweight concrete, lightweight aerated concrete, mortar, calcium silicate board, slate, gypsum board, etc., as well as an adhesive, a paint binder for exterior and interior use of structures and building materials, a paper processing agent, a fiber processing agent, a cosmetic, etc., by blending it with other resins, pigments, fillers, matting agents, antioxidants, UV absorbers, antifreeze agents, pH adjusters, preservatives, defoaming agents, antibacterial agents, antifungal agents, light stabilizers, antistatic agents, plasticizers, flame retardants, thickeners, surfactants, film-forming aids, and other resins.

[0047] The resin composition containing the silicone-vinyl acetate copolymer resin of the present invention, or a dispersion containing the resin composition, can be used as a coating agent. In this case, the coating composition is obtained by mixing and dissolving the silicone-vinyl acetate copolymer resin with other components using known mixing and preparation methods such as a propeller-type stirrer, homogenizer, ball mill, or bead mill. When the coating composition is applied, immersed, or dried on one or both sides of a substrate such as glass or resin, it can impart sliding properties and adhesion to the substrate. [Examples]

[0048] The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the following manufacturing examples and examples. Furthermore, the molecular weights described below are weight-average molecular weights (Mw) determined by viscosity measurement from the specific viscosity of a toluene solution of organopolysiloxane at a concentration of 1 g / 100 ml.

[0049] [Example 1] Dissolve 500g of octamethylcyclotetrasiloxane, 2.5g of γ-methacryloxypropylmethyldimethoxysilane, and 5g of sodium lauryl sulfate in 45g of pure water, and dissolve 5g of dodecylbenzenesulfonic acid in 45g of pure water in a 2L polyethylene beaker. Emulsify uniformly using a homomixer, then gradually add 400g of water to dilute, and apply a pressure of 300kgf / cm².2 The mixture was passed twice through a high-pressure homogenizer to obtain a homogeneous white emulsion. This emulsion was transferred to a 2 L glass flask equipped with a stirrer, thermometer, and reflux condenser, and polymerization was carried out at 55°C for 24 hours. After aging at 20°C for 24 hours, it was neutralized to pH 7 with a 10% sodium carbonate aqueous solution. After drying at 105°C for 3 hours, the non-volatile content (solids) of the emulsion was 45%, and the organopolysiloxane in the emulsion was a non-flowing, soft gel. The viscosity of the toluene solution of this silicone composition indicated a structure represented by formula (1) with a molecular weight of approximately 250,000. The structure of the organopolysiloxane obtained by the above polymerization reaction is 1 1H-NMR (frequency 600 MHz, room temperature, 128 integration cycles) and 29 Confirmed by Si-NMR (frequency 600 MHz, room temperature, 5000 integrating cycles) (instrument name: JNM-ECA600, measurement solvent: CDCl3). 1580g of a 10% aqueous solution of polyvinyl alcohol (saponification degree 98.5 mol%, degree of polymerization 500) was added to this solution, and 1053g of vinyl acetate was added dropwise over 3 to 5 hours at 80°C using an initiator to copolymerize vinyl acetate grafts onto the silicone composition, obtaining a silicone-vinyl acetate copolymer resin emulsion with a non-volatile content of 30%. The presence of polyvinyl alcohol in the obtained resin emulsion was confirmed by FT-IR (ATR method) [instrument name: IR Affinity-1s (Shimadzu Corporation)] and GCMS [instrument name: GCMS-QP2010 Ultra (Shimadzu Corporation)].

[0050] [Examples 2-4] A silicone-vinyl acetate copolymer resin emulsion with 30% non-volatile content was obtained by the same method as in Example 1, except that the amounts of (A) to (C) were replaced with those shown in Table 1.

[0051] [Comparative Example 1] Dissolve 500g of octamethylcyclotetrasiloxane, 2.5g of γ-methacryloxypropylmethyldimethoxysilane, and 5g of sodium lauryl sulfate in 45g of pure water, and dissolve 5g of dodecylbenzenesulfonic acid in 45g of pure water in a 2L polyethylene beaker. Emulsify uniformly using a homomixer, then gradually add 400g of water to dilute, and apply a pressure of 300kgf / cm². 2 The mixture was passed twice through a high-pressure homogenizer to obtain a homogeneous white emulsion. This emulsion was transferred to a 2 L glass flask equipped with a stirrer, thermometer, and reflux condenser, and polymerization was carried out at 55°C for 24 hours. After aging at 20°C for 24 hours, it was neutralized to pH 7 with a 10% sodium carbonate aqueous solution. After drying at 105°C for 3 hours, the non-volatile content (solids) of the emulsion was 45%, and the organopolysiloxane in the emulsion was a non-flowing, soft gel. Based on the viscosity of the toluene solution, the silicone composition had a structure represented by formula (1) with a molecular weight of approximately 250,000. To this, 26 g of polyoxyethylene alkyl ether was added, and 1053 g of vinyl acetate was added dropwise over 3 to 5 hours while the reaction was carried out at 80°C using an initiator to copolymerize vinyl acetate grafts onto the above silicone composition, obtaining a silicone-vinyl acetate copolymer resin emulsion with a non-volatile content of 30%.

[0052] [Comparative Example 2] Dissolve 500g of octamethylcyclotetrasiloxane, 46g of vinylmethyldimethoxysilane, and 5g of sodium lauryl sulfate in 45g of pure water, and dissolve 5g of dodecylbenzenesulfonic acid in 45g of pure water in a 2L polyethylene beaker. Emulsify uniformly using a homomixer, then gradually add 450g of water to dilute, and apply a pressure of 300kgf / cm². 2The mixture was passed twice through a high-pressure homogenizer to obtain a homogeneous white emulsion. This emulsion was transferred to a 2 L glass flask equipped with a stirrer, thermometer, and reflux condenser, and polymerization was carried out at 55°C for 24 hours. After aging at 10°C for 24 hours, it was neutralized to pH 7 with a 10% sodium carbonate aqueous solution. After drying at 105°C for 3 hours, the non-volatile content (solids) of the emulsion was 45%, and the organopolysiloxane in the emulsion was a non-flowing, soft gel. Based on the viscosity of the toluene solution, the silicone composition had a structure represented by formula (1) with a molecular weight of approximately 400,000. To this, 23 g of polyoxyethylene alkyl ether was added, and 1151 g of vinyl acetate was added dropwise over 3 to 5 hours while the reaction was carried out at 80°C using an initiator to copolymerize vinyl acetate graft onto the above silicone composition, obtaining a silicone-vinyl acetate copolymer resin emulsion with a non-volatile content of 30%.

[0053] [Comparative Example 3] Dissolve 500g of octamethylcyclotetrasiloxane, 1.1g of vinylmethyldimethoxysilane, and 5g of sodium lauryl sulfate in 45g of pure water, and dissolve 5g of dodecylbenzenesulfonic acid in 45g of pure water in a 2L polyethylene beaker. Emulsify uniformly using a homomixer, then gradually add 400g of water to dilute, and apply a pressure of 300kgf / cm². 2 The mixture was passed twice through a high-pressure homogenizer to obtain a homogeneous white emulsion. This emulsion was transferred to a 2 L glass flask equipped with a stirrer, thermometer, and reflux condenser, and polymerization was carried out at 55°C for 24 hours. After aging at 10°C for 24 hours, it was neutralized to pH 7 with a 10% sodium carbonate aqueous solution. After drying at 105°C for 3 hours, the non-volatile content (solids) of the emulsion was 45%, and the organopolysiloxane in the emulsion was a non-flowing, soft gel. Based on the viscosity of the toluene solution, the silicone composition had a structure represented by formula (1) with a molecular weight of approximately 400,000. To this, 21 g of polyoxyethylene alkyl ether was added, and 1051 g of vinyl acetate was added dropwise over 3 to 5 hours while the reaction was carried out at 80°C using an initiator to copolymerize vinyl acetate graft onto the above silicone composition, obtaining a silicone-vinyl acetate copolymer resin emulsion with a non-volatile content of 30%.

[0054] The emulsions obtained in Examples 1-4 and Comparative Examples 1-3 were evaluated using the following method. The results are shown in Table 1.

[0055] <Graft points> The graft points were calculated using the following formula. • Mass of silane coupling agent / Molecular weight of silane coupling agent = A • Calculation of molecular weight of organopolysiloxane: Mass of siloxane / Molecular weight of organopolysiloxane = B The value of "A / B" is defined as the number of graft points. For example, in the silicone-vinyl acetate copolymer resin emulsion shown in Manufacturing Example 1, A = 2.5 / 232 = 0.0108 mol ·B=(500+2.5) / 250,000=0.00201mol Since "A / B ≈ 5", the number of graft points is "5". The number of graft points can be adjusted by the amount of silane coupling agent used.

[0056] <Method for measuring solid content> Approximately 1 g of the sample was accurately weighed onto an aluminum foil dish, placed in a drying oven maintained at approximately 105°C, heated for 1 hour, then removed from the oven and allowed to cool in a desiccator. The weight of the dried sample was measured, and the evaporation residue was calculated using the following formula.

number

[0057] <Viscosity measurement method> The sample temperature was maintained at 23±0.5℃ and measured using a BM-type viscometer (No. 1 rotor, 6 rpm).

[0058] <Measurement of static and dynamic friction coefficients> The emulsion compositions of each example and comparative example were applied to a PET film using a bar coater, and dried at 105°C for 3 minutes to form a coating film approximately 10 μm thick when dry. Using a HEIDON TYPE-38 (manufactured by Shinto Kagaku Co., Ltd.), a 30g metal indenter was brought into perpendicular contact with the above coating and moved at a speed of 3cm / min. The frictional force was measured, and the coefficient of friction was calculated from the frictional force. Under the above conditions, the preferred range for static and dynamic friction coefficients is a static friction coefficient of 0.3 or less and a dynamic friction coefficient of 0.20 or less.

[0059] <Water and chemical resistance> The emulsion compositions of each example and comparative example were poured into PP trays and dried at 40°C for 24 hours to form a film approximately 1 mm thick when dry. The formed film was molded to 1 inch x 1 inch to obtain test specimens for evaluation. 100g of each solvent (water, methanol, DMF) was measured and placed in a glass bottle. The test specimens, whose mass had been measured, were then placed in the bottles and stirred with a stirrer for 1 hour. After 1 hour, the mixture was filtered through a 300-mesh filter, dried at 40°C for 24 hours, and the mass was measured again. The insolubility (%) was calculated from the mass loss.

[0060] <Adhesion to substrate> The emulsion compositions of each example and comparative example were applied to a PET film using a bar coater, and dried at 105°C for 3 minutes to form a coating film approximately 10 μm thick when dry. The paint film was scratched with a cutter, and the adhesion was visually evaluated by rubbing this area back and forth 10 times with a finger. ○: No peeling from the substrate. ×: Peeling from the substrate present.

[0061] <Scratch resistance> The emulsion compositions of each example and comparative example were applied to a PET film using a bar coater, and dried at 105°C for 3 minutes to form a coating film approximately 10 μm thick when dry. The scratch resistance of a coated PET film was measured using a JSPS friction tester (manufactured by Yasuda Seiki Seisakusho) with a 98N load applied and a cotton cloth attached to a metal contact object. The test was performed up to 1000 times, and the number of cycles until the coating was damaged was visually confirmed.

[0062] <Bleedout> The emulsion compositions of each example and comparative example were poured into a PP tray and dried at 40°C for 24 hours to form a film approximately 1 mm thick when dry. The state of silicone bleed-out on the film surface over time was visually observed. ○: No bleed-out was observed. △: Slight bleed-out was observed. ×: Significant bleed-out was observed.

[0063] [Table 1]

[0064] As shown in Table 1 above, the emulsion compositions containing silicone-acrylic copolymer resins in Comparative Examples 1 to 3 exhibited poor solvent resistance. In contrast, the silicone-vinyl acetate copolymer resin emulsion compositions of Example 1 all provided coating films with excellent sliding properties, adhesion, solvent resistance, and scratch resistance.

Claims

1. A resin composition comprising (A) a copolymer resin of organopolysiloxane units derived from an organopolysiloxane represented by the following general formula (1) and (B) vinyl acetate units, and (C) polyvinyl alcohol, characterized in that the mass ratio of the (A) organopolysiloxane units to the (B) vinyl acetate units is (A):(B) = 10:90 to 95:5, and the mass ratio of the (B) vinyl acetate units to the (C) polyvinyl alcohol is 100:15 to 50. 【Chemistry 1】 (In the formula, R 1 R is an identical or different unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, 2 R is a mercapto group, an acryloxy group, or a C1-C6 alkyl group substituted with a methacryloxy group, or a vinyl group. However, the above R １ It is not a vinyl group. Also, X is the same or different unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a hydroxyl group, and Y is a hydroxyl group, X, or -[O-Si(X)] 2 ] d -X represents the same or different group, and at least one of them in Y is a hydroxyl group or -[O-Si(X)] ２ The group is represented by ]d-X. However, the above X is not a vinyl group. Also, X, Y and -[O-Si(X) 2 ] d In Y represented by -X, at least two X groups are hydroxyl groups. Z is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydroxyl group. a is a positive number between 0 and 1,000, b is a positive number between 100 and 10,000, c is a positive number between 1 and 10, and d is a positive number between 1 and 1,000.

2. The resin composition according to claim 1, in the form of an emulsion having a viscosity (at 25°C) of 1 to 500 mPa·s.

3. The resin composition according to claim 1 or 2, wherein the weight-average molecular weight (Mw) of the organopolysiloxane represented by formula (1) above, determined by viscosity measurement, is 10,000 to 1,000,000.

4. The resin composition according to claim 1 or 2, wherein the organopolysiloxane represented by formula (1) above is a polymer of a cyclic organosiloxane, an α,ω-dihydroxysiloxane oligomer, an α,ω-dialkoxysiloxane oligomer, or an alkoxysilane and a silane coupling agent represented by the following general formula (2). R 3 (4-e-f) R 4 f Si(OR 5 ) e (2) (In the formula, R 3 R is a C1-C6 alkyl group substituted with a mercapto group, an acryloxy group, or a methacryloxy group, 4 R is an alkyl group having 1 to 4 carbon atoms. 5 (where e is an alkyl group having 1 to 4 carbon atoms, e is 2 or 3, f is 0 or 1, and e+f is 2 or 3.)

5. The resin composition according to claim 1 or 2, which is used as a product selected from the group consisting of coating agents, fiber treatment agents, adhesives, paints, and cosmetics.

6. A dispersion characterized by comprising the resin composition according to claim 1 or 2.

7. A method for producing a resin composition, characterized by emulsion polymerization of (A-1) an organopolysiloxane represented by the following general formula (1) and (B-1) vinyl acetate in a mass ratio of (A-1):(B-1) = 10:90 to 95:5, and further polymerization during emulsion polymerization with 15 to 50 parts by mass of (C) polyvinyl alcohol in solid content per 100 parts by mass of (B-1) vinyl acetate to obtain a resin emulsion. 【Chemistry 2】 (In the formula, R 1 R is an identical or different unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, 2 R is a mercapto group, an acryloxy group, or a C1-C6 alkyl group substituted with a methacryloxy group, or a vinyl group. However, the above R １ It is not a vinyl group. Also, X is the same or different unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a hydroxyl group, and Y is a hydroxyl group, X, or -[O-Si(X)] 2 ] d -X represents the same or different group, and at least one of them in Y is a hydroxyl group or -[O-Si(X)] ２ The group is represented by ]d-X. However, the above X is not a vinyl group. Also, X, Y and -[O-Si(X) 2 ] d In Y represented by -X, at least two X groups are hydroxyl groups. Z is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydroxyl group. a is a positive number between 0 and 1,000, b is a positive number between 100 and 10,000, c is a positive number between 1 and 10, and d is a positive number between 1 and 1,000.

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