Silane-modified copolymer, method for producing the same and composition containing the same

Abstract

Provided is a silane-modified copolymer comprising: a constituent unit expressed by formulae (1) and (2) below; and an epoxy-group containing constituent unit. (In the formulae, R1 independently represents an alkyl group having 1-10 carbon atoms or an aryl group having 6-20 carbon atoms, R2 independently represents an alkyl group having 1-10 carbon atoms or an aryl group having 6-20 carbon atoms, m represents an integer of 1-3, and the asterisk * represents a bond to an adjacent constituent unit. The constituent units can be arranged in any order.)

Description

[Technical Field]

[0001] The present invention relates to a silane-modified copolymer, a method for producing the same, and a composition containing the same. More specifically, the present invention relates to a copolymer having an epoxy group and a hydrolyzable silyl group and also having a polybutadiene skeleton, a method for producing the same, and a composition containing the copolymer. [Background technology]

[0002] Organosilicon compounds that have both a functional group reactive with organic materials, such as an epoxy group, an amino group, an acryloyl group, a methacryloyl group, a mercapto group, an isocyanate group, or an acid anhydride residue, and a functional group reactive with inorganic materials, such as a hydrolyzable silyl group, are generally called silane coupling agents, and act as a medium for bonding organic and inorganic materials that are normally difficult to bond. Taking advantage of these properties, silane coupling agents are widely used as modifiers for organic and inorganic materials, adhesion aids used to bond both materials, and various additives.

[0003] Among these, 3-glycidoxypropyltrimethoxysilane is a common silane coupling agent with an epoxy functional group, and its effectiveness has been proven in a wide range of applications. However, since it is a monomer and is highly volatile, there are safety concerns, so there is a demand for less volatile materials. Prior art documents related to the present invention include the following: [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2009-191155 Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a silane-modified copolymer having an epoxy group, which has high adhesion to a substrate and low volatility. [Means for solving the problem]

[0006] As a result of extensive research aimed at solving the above problems, the present inventors have found that a specific copolymer having an epoxy group and a hydrolyzable silyl group as well as a polybutadiene skeleton has low volatility and high adhesion to substrates, and have thus completed the present invention.

[0007] That is, the present invention provides: 1. The following formulas (1) and (2) [ka] (wherein an asterisk * indicates a bond to an adjacent structural unit, and in formula (2), R 1 are each independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R 2 are each independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms, and m is an integer of 1 to 3. However, the order of each structural unit is arbitrary. a silane-modified copolymer containing a structural unit represented by the formula: 2. The epoxy group-containing structural unit is represented by the following formula (3) and formula (4): [ka] (In the formula, the asterisk * has the same meaning as above.) 2. The silane-modified copolymer according to 1, wherein the structural unit is one or more selected from structural units represented by 3. The following equations (1) and (5) [ka] (In the formula, the asterisk * has the same meaning as above.) and an epoxy group-containing structural unit (however, the order of the structural units is arbitrary), and a copolymer containing a structural unit represented by the following formula (6): [ka] (In the formula, R 1 , R 2 and m have the same meaning as above. 2. A method for producing the silane-modified copolymer according to 1, comprising a step of subjecting an organosilicon compound represented by the formula: 4. The method for producing a silane-modified copolymer according to 3, wherein the epoxy group-containing structural unit is at least one selected from structural units represented by the following formulas (3) and (4): [ka] (In the formula, the asterisk * has the same meaning as above.) 5. A composition comprising the silane-modified copolymer according to 1 or 2. 6. The composition according to 5, which contains an organopolysiloxane to provide. [Effects of the Invention]

[0008] The silane-modified copolymer of the present invention has an epoxy group, a hydrolyzable silyl group, and a polybutadiene skeleton, is low in volatility, and can exhibit high adhesiveness when blended in a composition. DETAILED DESCRIPTION OF THE INVENTION

[0009] The present invention will be specifically described below. [1] Silane-modified copolymer The silane-modified copolymer according to the present invention contains a polybutadiene-constituting unit represented by the following formula (1), a hydrolyzable silyl group-containing structural unit represented by the following formula (2), and an epoxy group-containing structural unit. The order of the structural units is arbitrary.

[0010] [ka] (wherein the asterisk * indicates a bond to an adjacent building block.)

[0011] Here, in the above formula (2), R 1 are each independently an alkyl group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, and more preferably 1 to 6 carbon atoms, or an aryl group having 6 to 20 carbon atoms, preferably 6 to 15 carbon atoms, and more preferably 6 to 10 carbon atoms; R 2 are each independently an alkyl group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, and more preferably 1 to 6 carbon atoms, or an aryl group having 6 to 20 carbon atoms, preferably 6 to 15 carbon atoms, and more preferably 6 to 10 carbon atoms, and m is an integer of 1 to 3.

[0012] R 1 and R 2 The alkyl group having 1 to 10 carbon atoms may be linear, branched, or cyclic, and specific examples thereof include methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups. R 1 and R 2 Specific examples of the aryl group having 6 to 20 carbon atoms include phenyl, α-naphthyl, and β-naphthyl groups.

[0013] Among these, R 1 As the alkyl group, a linear alkyl group is preferred, and a methyl group or an ethyl group is more preferred. Also, R 2 As the alkyl group, a linear alkyl group is preferred, and a methyl group or an ethyl group is more preferred. m is an integer of 1 to 3, preferably 2 or 3, and more preferably 3.

[0014] In the silane-modified copolymer of the present invention, the epoxy group-containing structural unit is not particularly limited in structure as long as it contains an epoxy group and can constitute a copolymer together with the structural units represented by the above formulas (1) and (2). However, one or more structural units selected from the structural units represented by the following formulas (3) and (4) are preferred, and both of these are more preferred.

[0015] [ka] (In the formula, the asterisk * has the same meaning as above.)

[0016] In the silane-modified copolymer of the present invention, the total number of the structural units represented by the above formula (1) and formula (2) among all the structural units constituting the silane-modified copolymer is preferably 30 mol % or more, more preferably 40 mol % or more, and although there is no particular upper limit, it is preferably 90 mol % or less. In particular, in order to further enhance the effect of the silane-modified copolymer of the present invention as an adhesive aid, the proportion of structural units having a hydrolyzable silyl group represented by the above formula (2) among the total number of structural units constituting the silane-modified copolymer is preferably 2 mol% or more, more preferably 4 mol% or more, and although there is no particular upper limit, it is preferably 25 mol% or less. The total proportion of the epoxy group-containing structural units represented by the above formulas (3) and (4) is preferably 0.5 mol% or more, more preferably 1 mol% or more. There is no particular upper limit, but it is preferably 30 mol% or less. The total of the structural units constituting the silane-modified copolymer is 100 mol%.

[0017] The silane-modified copolymer of the present invention may contain other structural units in addition to the structural units represented by the above formulas (1) to (4). Specific examples of other structural units include a structural unit represented by the following formula (5) and a structural unit represented by the following formula (7). When other structural units are contained, the total proportion of these structural units is preferably 50 mol % or less, and more preferably 45 mol % or less, of the total number of structural units constituting the silane-modified copolymer. Even when other structural units are contained, the order of each structural unit is arbitrary. Also in this case, the total of the structural units constituting the silane-modified copolymer is 100 mol %.

[0018] [ka] (In the formula, the asterisk * has the same meaning as above.)

[0019] The number average molecular weight of the silane-modified copolymer of the present invention is not particularly limited, but is preferably at least 500, more preferably at least 1,000. The upper limit of the number average molecular weight is preferably 10,000 or less, more preferably 5,000 or less. The number average molecular weight is a polystyrene equivalent value determined by gel permeation chromatography (GPC).

[0020] [2] Manufacturing method The silane-modified copolymer of the present invention can be obtained, for example, by subjecting a raw material copolymer containing structural units represented by the following formulas (1) and (5) and an epoxy group-containing structural unit to a hydrosilylation reaction with an organosilicon compound represented by the following formula (6) in the presence of a platinum compound-containing catalyst, provided that the order of the structural units is arbitrary.

[0021] [ka] (wherein, asterisk *, R 1 , R 2 and m have the same meaning as above.

[0022] In the raw material copolymer, the epoxy group-containing structural unit is not particularly limited in structure as long as it contains an epoxy group and can constitute a copolymer together with the structural units represented by the above formulas (1) and (5). However, one or more structural units selected from the structural units represented by the following formulas (3) and (4) are preferred, and both of these are more preferred.

[0023] [ka] (In the formula, the asterisk * has the same meaning as above.)

[0024] Copolymers containing the structural units represented by the above formulas (1) and (5) and epoxy group-containing structural units are available as commercially available products, such as Ricon 657 (manufactured by Cray Valley), JP-100, JP-200 (all manufactured by Nippon Soda Co., Ltd.), Epolead PB4700 (manufactured by Daicel Corporation), and Adeka Cizer BF-1000 (manufactured by Adeka Corporation). Furthermore, copolymers in which some of the unsaturated bonds of copolymers having structural units represented by the above formulas (1) and (5) have been epoxidized, such as Ricon 130 (manufactured by Cray Valley), can also be used.

[0025] On the other hand, examples of the organosilicon compound represented by the above formula (6) include trimethoxysilane, triethoxysilane, dimethoxymethylsilane, and diethoxymethylsilane.

[0026] The reaction ratio of the raw material copolymer and the organosilicon compound represented by formula (6) is preferably 0.01 to 3 moles, and more preferably 0.05 to 1 mole, of the organosilicon compound represented by formula (6) per mole of the structural unit represented by formula (5) in the raw material copolymer.

[0027] The platinum compound-containing catalyst used in the hydrosilylation reaction is not particularly limited, and specific examples include chloroplatinic acid, an alcohol solution of chloroplatinic acid, a toluene or xylene solution of a platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex, tetrakistriphenylphosphine platinum, dichlorobistriphenylphosphine platinum, dichlorobisacetonitrile platinum, dichlorobisbenzonitrile platinum, dichlorocyclooctadiene platinum, and supported catalysts such as platinum-carbon, platinum-alumina, and platinum-silica. Among these, zero-valent platinum complexes are preferred from the viewpoint of selectivity during hydrosilylation, and a toluene or xylene solution of a platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex is more preferred. The amount of platinum compound-containing catalyst used is not particularly limited, but from the viewpoints of reactivity and productivity, it is preferred that the amount of platinum atoms contained in the catalyst be 1×10 per mole of the organosilicon compound represented by formula (6). -8 ~1×10 -2 The preferred amount is 1 x 10 -7 ~1×10 -3 A molar amount is more preferred.

[0028] In the hydrosilylation reaction, a co-catalyst may be used. Examples of the co-catalyst include ammonium salts of inorganic acids, acid amide compounds, and carboxylic acids.

[0029] Specific examples of ammonium salts of inorganic acids include ammonium chloride, ammonium sulfate, ammonium amidosulfate, ammonium nitrate, monoammonium dihydrogen phosphate, diammonium hydrogen phosphate, triammonium phosphate, ammonium diphosphite, ammonium carbonate, ammonium hydrogen carbonate, ammonium sulfide, ammonium borate, and ammonium fluoroborate. Among these, ammonium salts of inorganic acids having a pKa of 2 or more are preferred, and ammonium carbonate and ammonium hydrogen carbonate are more preferred.

[0030] Specific examples of acid amide compounds include formamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, propionamide, acrylamide, malonamide, succinamide, maleamide, fumaramide, benzamide, phthalamide, palmitic acid amide, and stearic acid amide.

[0031] Specific examples of carboxylic acids include acetic acid, propionic acid, butyric acid, methoxyacetic acid, pentanoic acid, caproic acid, heptanoic acid, octanoic acid, lactic acid, glycolic acid, etc., and among these, formic acid, acetic acid, and lactic acid are preferred, with acetic acid being more preferred.

[0032] When a co-catalyst is used, there is no particular restriction on the amount used. However, from the viewpoints of reactivity, selectivity, and cost, it is preferable to use 1×10 -5 ~1×10 -1 Molar is preferred, 1 x 10 -4 ~5×10 -1 Molar is more preferred.

[0033] The above reaction proceeds without a solvent, but a solvent can also be used. Specific examples of usable solvents include hydrocarbon solvents such as pentane, hexane, cyclohexane, heptane, isooctane, benzene, toluene, and xylene; ether solvents such as diethyl ether, tetrahydrofuran, and dioxane; ester solvents such as ethyl acetate and butyl acetate; aprotic polar solvents such as N,N-dimethylformamide; and chlorinated hydrocarbon solvents such as dichloromethane and chloroform. These solvents may be used alone or in combination of two or more.

[0034] The reaction temperature for the hydrosilylation reaction is not particularly limited, and the reaction can be carried out at temperatures from 0°C to under heating, preferably from 0 to 200°C. To obtain an appropriate reaction rate, it is preferable to carry out the reaction under heating. From this viewpoint, the reaction temperature is more preferably 40 to 110°C, and even more preferably 40 to 90°C. The reaction time is not particularly limited, and is usually about 1 to 60 hours, preferably 1 to 30 hours, and more preferably 1 to 20 hours.

[0035] Generally, epoxy group-containing organosilicon compounds have adhesive properties to inorganic substrates such as glass and metals, but the silane-modified copolymer of the present invention can be suitably used as an adhesion improver for organic substrates such as resins and rubbers in addition to inorganic substrates such as glass and metals.

[0036] [3] Composition The composition of the present invention contains the above-mentioned silane-modified copolymer. The silane-modified copolymer of the present invention is a compound with a large molecular weight and contains multiple hydrolyzable silyl groups and epoxy groups per molecule. Therefore, by incorporating a predetermined amount of the copolymer into silicone compositions such as epoxy resin compositions, urethane resin compositions, acrylic resin compositions, polyimide resin compositions, silicone resin compositions, and modified silicone resin compositions, it is expected to provide adhesion and bonding properties equal to or greater than those of conventional epoxy group-containing organosilicon compounds. In particular, it is preferably incorporated into silicone compositions. The content of the silane-modified copolymer in the composition of the present invention is not particularly limited, but is preferably 0.1 to 20% by mass, more preferably 0.1 to 10% by mass, of the total composition.

[0037] When the silane-modified copolymer of the present invention is blended with a silicone composition, any known silicone composition can be used, such as one containing a linear organopolysiloxane whose molecular chain is terminally blocked with hydroxyl groups and a curing catalyst.

[0038] Specific examples of linear organopolysiloxanes in which both molecular chain terminals are blocked with hydroxyl groups include dimethylpolysiloxanes in which both molecular chain terminals are blocked with hydroxyl groups, methylphenylpolysiloxanes in which both molecular chain terminals are blocked with hydroxyl groups, and methylvinylpolysiloxanes in which both molecular chain terminals are blocked with hydroxyl groups. These organopolysiloxanes preferably have a viscosity at 25°C of 300 to 500,000 mPa·s, more preferably 500 to 100,000 mPa·s, and even more preferably 1,000 to 80,000 mPa·s. The viscosity can be measured using a rotational viscometer. These organopolysiloxanes may be used alone or in combination of two or more types with different structures or molecular weights.

[0039] As the curing catalyst, it is preferable to use an organic metal catalyst. Examples of the organic metal catalyst include alkyl tin ester compounds such as dibutyltin diacetate, dibutyltin dilaurate, and dibutyltin dioctoate; titanate esters or titanium chelate compounds such as tetraisopropoxytitanium, tetra-n-butoxytitanium, tetrakis(2-ethylhexoxy)titanium, dipropoxybis(acetylacetonato)titanium, and titanium isopropoxyoctylene glycol; zinc naphthenate, zinc stearate, zinc-2-ethyloctoate; iron-2-ethylhexoate; cobalt-2-ethylhexoate, cobalt naphthenate; manganese-2-ethylhexoate; alkoxyaluminum compounds, and aluminum chelate compounds. These may be used alone or in combination of two or more. The amount of the curing catalyst to be added is preferably 0.01 to 15 parts by mass, more preferably 0.01 to 5 parts by mass, per 100 parts by mass of the organopolysiloxane.

[0040] The composition of the present invention may contain, as needed, hydrolyzable silanes such as methyltri(methylethylketoxime)silane and / or partial hydrolysis condensates thereof, fillers such as silica, silane coupling agents, organopolysiloxanes other than those mentioned above, and the like.

[0041] The composition of the present invention can be prepared by mixing the above components in a conventional manner.

[0042] A coated substrate can be obtained by applying the composition of the present invention to the surface of various substrates and curing it to form a coating layer, and an adhesive laminate can be obtained by applying the composition of the present invention to the surface of a substrate, laminating another substrate on top of it, and then curing the composition to form an adhesive layer. The method for applying the composition of the present invention is not particularly limited, and specific examples thereof include known methods such as spray coating, spin coating, dip coating, roller coating, brush coating, bar coating, and flow coating, and any method can be appropriately selected and used.

[0043] The substrate is not particularly limited, and specific examples include organic resin substrates such as polyester resins such as polypropylene resin, poly(ethylene terephthalate), and poly(butylene terephthalate), acrylic resins such as polystyrene resin and poly(methyl methacrylate), polyamide resins such as polyethylene resin and nylon, acrylonitrile-butadiene-styrene resin, and polyphenylene sulfide resin; rubber substrates such as urethane rubber and butadiene rubber; metal substrates; painted surfaces; glass; ceramics; concrete; slate boards; textiles; inorganic fillers such as (hollow) silica, titania, zirconia, and alumina; and glass fiber products such as glass fiber, glass cloth, glass tape, glass mat, and glass paper. The shape of the substrate is not particularly limited.

[0044] The curing reaction temperature and time can be appropriately changed depending on the substrate used, etc. The curing reaction temperature is usually preferably room temperature around 23°C from the viewpoint of workability, etc., but to promote the curing reaction, the curing may be performed by heating within a range not exceeding the heat resistance temperature of the substrate used. The curing reaction time is usually about 1 minute to 1 week from the viewpoint of workability, etc. [Example]

[0045] The present invention will be explained in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. In the following examples, "parts" means parts by mass. The molecular weight is the number average molecular weight calculated as polystyrene by GPC measurement. The viscosity is the value measured at 25°C using a rotational viscometer.

[0046] [1] Preparation of silane-modified copolymer [Example 1-1] Into a 1 L separable flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer, 540 g of Ricon 657 (manufactured by CRAY VALLEY, number average molecular weight 2,200, composed of structural units represented by the following formulas (1), (3), (4), and (5), (1) / [(3)+(4)] / (5)=30 / 20 / 50 (molar ratio)) and 10 g of a toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (1 x 10 platinum atoms). -5 244 g of trimethoxysilane was added dropwise over 1 hour at an internal temperature of 75-85°C. The mixture was then aged for 3 hours at 80°C. After aging, the mixture was concentrated under reduced pressure and filtered to obtain a pale yellow liquid, silane-modified copolymer A, with a viscosity of 300,000 mPa·s and a number-average molecular weight of 3,200. The resulting silane-modified copolymer A was composed of structural units represented by the following formulas (1), (2'), (3), (4), and (5), with a molar ratio of (1) / [(3)+(4)] / (2') / (5)=30 / 20 / 20 / 30.

[0047] [ka] (In the formula, the asterisk * has the same meaning as above.)

[0048] [Example 1-2] Into a 1 L separable flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer, 540 g of Ricon 657 (manufactured by CRAY VALLEY, number average molecular weight 2,200, composed of structural units represented by the above formulas (1), (3), (4), and (5), with a molar ratio of (1) / [(3)+(4)] / (5)=30 / 20 / 50) and 10 g of a toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (1 x 10 platinum atoms). -5(mol) was added, and 122 g of trimethoxysilane was added dropwise over 1 hour at an internal temperature of 75-85°C. The mixture was then aged for 3 hours at 80°C. After aging, the mixture was concentrated under reduced pressure and filtered to obtain silane-modified copolymer B, a pale yellow liquid with a viscosity of 270,000 mPa·s and a number-average molecular weight of 2,700. The obtained silane-modified copolymer B was composed of structural units represented by the above formulas (1), (2'), (3), (4), and (5), with a molar ratio of (1) / [(3) + (4)] / (2') / (5) = 30 / 20 / 10 / 40.

[0049] [Examples 1-3] Into a 1-L separable flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer, 540 g of a partially epoxidized copolymer of Ricon 130 (manufactured by CRAY VALLEY) (number average molecular weight 2,700, composed of structural units represented by the above formulas (1), (3), (4), and (5), with a molar ratio of (1) / [(3)+(4)] / (5)=71 / 1 / 28)) and 100 g of a toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (1 x 10 platinum atoms). -5 (mol) was added, and 244 g of trimethoxysilane was added dropwise over 1 hour at an internal temperature of 75-85°C. This was followed by aging at 80°C for 3 hours. After aging, the mixture was concentrated under reduced pressure and filtered to obtain silane-modified copolymer C, a pale yellow liquid with a viscosity of 1,800 mPa·s and a number-average molecular weight of 3,800. The resulting silane-modified copolymer C was composed of structural units represented by the above formulas (1), (2'), (3), (4), and (5), with a molar ratio of (1) / [(3) + (4)] / (2') / (5) = 71 / 1 / 18 / 10.

[0050] [Examples 1-4] Into a 1-L separable flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer, 540 g of a partially epoxidized copolymer of Ricon 130 (manufactured by CRAY VALLEY) (number average molecular weight 2,700, composed of structural units represented by the above formulas (1), (3), (4), and (5), with a molar ratio of (1) / [(3)+(4)] / (5)=71 / 1 / 28)) and 100 g of a toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (1 x 10 platinum atoms). -5 (mol) was added, and 122 g of trimethoxysilane was added dropwise over 1 hour at an internal temperature of 75-85°C. The mixture was then aged for 3 hours at 80°C. After aging, the mixture was concentrated under reduced pressure and filtered to obtain silane-modified copolymer D, a pale yellow liquid with a viscosity of 1,800 mPa·s and a number-average molecular weight of 3,300. The obtained silane-modified copolymer D was composed of structural units represented by the above formulas (1), (2'), (3), (4), and (5), with a molar ratio of (1) / [(3) + (4)] / (2') / (5) = 71 / 1 / 9 / 19.

[0051] [Examples 1-5] Into a 1-L separable flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer, 540 g of a partially epoxidized copolymer of Ricon 130 (manufactured by CRAY VALLEY) (number average molecular weight 2,700, composed of structural units represented by the above formulas (1), (3), (4), and (5), with a molar ratio of (1) / [(3)+(4)] / (5)=71 / 1 / 28)) and 100 g of a toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (1 x 10 platinum atoms). -5 (mol) was added, and 61 g of trimethoxysilane was added dropwise over 1 hour at an internal temperature of 75-85°C. This was followed by aging at 80°C for 3 hours. After aging, the mixture was concentrated under reduced pressure and filtered to obtain silane-modified copolymer E, a pale yellow liquid with a viscosity of 1,700 mPa·s and a number-average molecular weight of 3,000. The resulting silane-modified copolymer E was composed of structural units represented by the above formulas (1), (2'), (3), (4), and (5), with a molar ratio of (1) / [(3) + (4)] / (2') / (5) = 71 / 1 / 5 / 23.

[0052] [2] Volatility evaluation of silane-modified copolymers Volatility was evaluated for the silane-modified copolymers A to E obtained in Examples 1-1 to 1-5 above, and the following organosilicon compound F (Comparative Example 1-1). Organosilicon compound F: 3-glycidoxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0053] The evaluation method was to drop 1 g of each compound into an aluminum dish, place it in a thermostatic chamber at 150°C for 3 hours in an open system, and then evaluate the remaining percentage as non-volatile content. The higher the non-volatile content, the lower the volatility of the compound. The evaluation results are shown in Table 1.

[0054] [Table 1]

[0055] As shown in Table 1, the silane-modified copolymers of the present invention obtained in Examples 1-1 to 1-5 are found to have low volatility. Therefore, the silane-modified copolymer of the present invention can suppress volatilization during high-temperature coating and can exhibit the required properties with the minimum necessary amount, making it economical.Furthermore, it can suppress contamination of peripheral equipment and is expected to improve productivity.

[0056] [3] Preparation of the composition [Example 2-1] 60 parts of dimethylpolysiloxane with a viscosity of 50,000 mPa·s and terminated at both molecular chain ends with hydroxyl groups, 25 parts of dimethylpolysiloxane with a viscosity of 100 mPa·s and terminated at both molecular chain ends with trimethylsilyl groups, and 10 parts of surface-treated silica were mixed under normal pressure for 30 minutes, then mixed again under reduced pressure for 15 minutes. 0.5 parts of silane-modified copolymer A and 4 parts of methyltri(methylethylketoxime)silane were added, and mixed at atmospheric pressure for 10 minutes, followed by mixing under reduced pressure for 30 minutes. After completing the vacuum mixing, 0.1 parts of dioctyltin dilaurate was added and mixed under reduced pressure for 60 minutes to obtain Composition I.

[0057] [Example 2-2] Composition II was prepared in the same manner as in Example 2-1, except that 0.5 parts of silane-modified copolymer B was added in place of silane-modified copolymer A.

[0058] [Example 2-3] Composition III was prepared in the same manner as in Example 2-1, except that 0.5 parts of silane-modified copolymer C was added in place of silane-modified copolymer A.

[0059] [Example 2-4] Composition IV was prepared in the same manner as in Example 2-1, except that 0.5 parts of silane-modified copolymer D was added in place of silane-modified copolymer A.

[0060] [Example 2-5] Composition V was prepared in the same manner as in Example 2-1, except that 0.5 parts of silane-modified copolymer E was added in place of silane-modified copolymer A.

[0061] [Comparative Example 2-1] Composition VI was prepared in the same manner as in Example 2-1, except that silane-modified copolymer A was not added.

[0062] [Comparative Example 2-2] Composition VII was prepared in the same manner as in Example 2-1, except that 0.5 parts of organosilicon compound F was added in place of silane-modified copolymer A.

[0063] [4] Evaluation of adhesive properties of the composition Each composition prepared in Examples 2-1 to 2-5 and Comparative Examples 2-1 and 2-2 was applied to a plate-shaped substrate (material: polyester resin, 6-nylon resin, urethane rubber, ABS resin), and after curing at 23°C and 50% RH for 7 days, the adhesiveness was confirmed.

[0064] Adhesion was tested according to the cross-cut method (25-square grid tape peel test) of JIS K-5600. The results were evaluated as follows: ○: adhesion (no peeling), △: partial peeling (30% or less peeled area), ×: peeling (more than 30% peeled area). The results are shown in Table 2 below.

[0065] [Table 2]

[0066] As shown in Table 2, the silane-modified copolymers of Examples 2-1 to 2-5 can exhibit adhesiveness equal to or greater than that of the conventional epoxy group-containing organosilicon compound (3-glycidoxypropyltrimethoxysilane) of Comparative Example 2-2.

Claims

1. The following formulas (1), (2) and (5) 【Chemistry 1】 (wherein an asterisk * indicates a bond to an adjacent constitutional unit, and in formula (2), R 1 are each independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms, R 2 are each independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms, and m is an integer of 1 to 3. However, the order of each structural unit is arbitrary. A silane-modified copolymer comprising a structural unit represented by the formula: and an epoxy group-containing structural unit.

2. The epoxy group-containing structural unit is represented by the following formula (3) and formula (4): 【Chemistry 2】 (In the formula, the asterisk * has the same meaning as above.) 2. The silane-modified copolymer according to claim 1, wherein the structural unit is one or more selected from the structural units represented by the formula:

3. A silane-modified copolymer according to claim 1, wherein the proportion of the constituent units represented by the above formula (2) among the total number of constituent units constituting the silane-modified copolymer is 2 mol% or more and 25 mol% or less.

4. A silane-modified copolymer according to claim 1, wherein the proportion of the constituent units represented by the above formula (5) among the total number of constituent units constituting the silane-modified copolymer is 10 mol% or more and 50 mol% or less.

5. The following formulas (1) and (5) 【Transformation 3】 (In the formula, the asterisk * has the same meaning as above.) and an epoxy group-containing structural unit (however, the order of the structural units is arbitrary), and a copolymer containing a structural unit represented by the following formula (6): 【Chemistry 4】 (In the formula, R 1 , R 2 and m have the same meanings as above. and an organosilicon compound represented by the formula (I) in the presence of a platinum compound-containing catalyst.

6. 6. The method for producing a silane-modified copolymer according to claim 5, wherein the epoxy group-containing structural unit is at least one selected from the structural units represented by the following formulas (3) and (4): 【Transformation 5】 (In the formula, the asterisk * has the same meaning as above.)

7. A composition comprising the silane-modified copolymer according to any one of claims 1 to 4.

8. The composition of claim 7, comprising an organopolysiloxane.

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