JP3199598B2 - Method for producing (meth) acryloyloxyl group-containing organopolysiloxane - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an electron beam-curable resin composition having excellent storage stability and easy purification.
The present invention relates to a method for producing a (meth) acryloyloxyl group-containing organopolysiloxane useful as a base polymer of a thermosetting resin composition or a photocurable resin composition.

[0002]

2. Description of the Related Art Conventionally known acryloyloxyl group-containing organopolysiloxane is a polymer having a relatively low molecular weight (for example, 2,000 or less in terms of polystyrene by GPC). On the other hand, if the molecular weight can be further increased, high-speed curing is possible and, for example, a thermosetting resin composition, an electron beam-curable resin composition, and a photocurable resin capable of forming a pattern used for a semiconductor circuit or the like. It is extremely useful as a base polymer for a conductive resin composition and the like. However, an acryloyloxyl group-containing organopolysiloxane having a molecular weight of 3,000 or more (in terms of polystyrene by GPC) has not yet been used as the base polymer.

In order to obtain such a high molecular weight acryloyloxyl group-containing organopolysiloxane by applying a conventionally known method, for example, an acryloyloxyl group-containing alkoxysilane and another alkoxysilane may be used depending on the intended molecular structure. Is subjected to co-hydrolysis, followed by condensation polymerization by heating. However, the acryloyloxyl group-containing organopolysiloxane having a high degree of polymerization obtained by this method is unstable because it has a large number of silanol groups, and becomes viscous and gels over time. Further, the thus obtained acryloyloxyl group-containing organopolysiloxane having a high degree of polymerization has hydrophilicity, so that it is difficult to remove water-soluble impurities by a solvent extraction method using an organic solvent and water, so that purification is difficult.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide excellent storage stability, which can be easily purified by washing with water,
An object of the present invention is to provide a production method capable of obtaining an organopolysiloxane having a high degree of polymerization having a (meth) acryloyloxyl group by a simple process.

[0005]

Means for Solving the Problems The present invention, (A) the following general formula _{(1): CH 2 = CR} 1 COO-C 3 H 6 -SiR 2 a (OR 3) 3-a (1) ( Formula Wherein R ¹ is a hydrogen atom or a methyl group, R ² is an unsubstituted or substituted monovalent hydrocarbon group, R ³ is an alkyl group, and a is an integer of 0 to 2) (Meth) acryloyloxypropylalkoxysilane;
The following general formula (2): R ⁴ _4-n Si (OR ⁵ ) _n (2) (where R ⁴ is an unsubstituted or substituted monovalent hydrocarbon group, R ⁵ is an alkyl group, and n Is an integer of from 1 to 4) in the presence of hydrochloric acid , followed by co-hydrolysis, followed by condensation polymerization to obtain a co-hydrolyzed condensation polymer having a silanol group; Reacting the co-hydrolyzed polycondensate with a silylating agent to silylate the silanol group, and comprising a (meth) acryloyloxyl group having an average molecular weight of 3,000 or more (in terms of polystyrene by GPC). This is a method for producing a contained organopolysiloxane.

Hereinafter, the present invention will be described in detail. (A) Co-hydrolysis / condensation polymerization step In the production method of the present invention, first, (meth) acryloyloxypropylalkoxysilane represented by the general formula (1) and alkoxysilane represented by the general formula (2) are used. Is co-hydrolyzed in the presence of hydrochloric acid and then polycondensed to obtain a co-hydrolyzed polycondensate having a silanol group.

Examples of the unsubstituted or substituted monovalent hydrocarbon group represented by R ² in the general formula (1) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group and a tert-butyl group. -Alkyl group such as butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group; cycloalkyl group such as cyclopentyl group, cyclohexyl group, cycloheptyl group; vinyl group, Allyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group,
Alkenyl groups such as hexenyl group and cyclohexenyl group;
Aryl groups such as phenyl group, tolyl group, xylyl group, naphthyl group and biphenyl group; aralkyl groups such as benzyl group, phenylethyl group, phenylpropyl group and methylbenzyl group; and bonded to carbon atoms of these groups A group in which part or all of hydrogen atoms are substituted with a halogen atom such as fluorine, chlorine, or bromine, a cyano group, and the like, for example, a chloromethyl group, a 2-bromoethyl group, a 3-chloropropyl group, a 3,3,3- Trifluoropropyl group, chlorophenyl group, fluorophenyl group, cyanoethyl group, 3,
Unsubstituted or substituted monovalent hydrocarbon groups having 1 to 12 carbon atoms, such as 3,4,4,5,5,6,6,6-nonafluorohexyl group.

The alkyl group represented by R ³ in the general formula (1) includes, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-
Butyl group, pentyl group, neopentyl group, hexyl group,
Examples include a heptyl group, an octyl group, a nonyl group, a decyl group, and a dodecyl group.

Specific examples of the (meth) acryloyloxypropylalkoxysilane represented by the general formula (1) include, for example, acryloyloxypropyldimethylmonomethoxysilane, acryloyloxypropyldimethylmonoethoxysilane, acryloyloxypropyldiphenylmonomethoxy (Meth) acryloyloxypropyldicarbyl monoalkoxysilanes such as silane, acryloyloxypropyldiphenylmonoethoxysilane, (2-methyl) acryloyloxypropyldimethylmonoethoxysilane; acryloyloxypropylmonomethyldimethoxysilane, acryloyloxypropylmonomethyldiethoxysilane , Acryloyloxypropylmonophenyldimethoxysilane, acryloyloxypropylmonoph (Meth) acryloyloxypropyl monocarbyl dialkoxysilanes such as nildiethoxysilane and (2-methyl) acryloyloxypropylmonomethyldiethoxysilane; acryloyloxypropyltrimethoxysilane, acryloyloxypropyltriethoxysilane, acryloyloxypropyltripropoxy Examples thereof include silane and (meth) acryloyloxypropyl trialkoxysilane such as (2-methyl) acryloyloxypropyltrimethoxysilane.
These can be used alone or in combination of two or more.

Examples of the unsubstituted or substituted monovalent hydrocarbon group represented by R ⁴ in the general formula (2) include the same as those described above for R ^2, and the alkyl group represented by R ⁵ includes ,
The same as the above R ³ can be mentioned. The general formula (2)
Specific examples of the alkoxysilane represented by, for example, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane,
Phenyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, diphenyldimethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, diphenyldiethoxysilane, trimethylmethoxysilane , Triethylmethoxysilane, triphenylmethoxysilane, trimethylethoxysilane, triethylethoxysilane,
And triphenylethoxysilane. Particularly preferred alkoxysilanes are those of general formula (2) wherein n is 2 or 3.

[0011] alkoxy cohydrolysis of silanes, lines in the presence of hydrochloric acid as catalysts of the general formula (1) and (2)
U.

The amount of hydrochloric acid used as a catalyst is usually 0.001 to 1.0 part by weight based on 100 parts by weight of the total amount of the alkoxysilanes of the general formulas (1) and (2). Co-hydrolysis may be usually performed at 0 to 50 ° C. The amount of each reaction component subjected to co-hydrolysis is preferably the amount of the alkoxysilane represented by the general formula (2) per mole of (meth) acryloyloxypropylalkoxysilane represented by the general formula (1), , 0.1 to 20 mol, more preferably 0.5 to 5.0 mol.

The (meth) acryloyloxypropylalkoxysilane represented by the general formula (1) includes (meth) acryloyloxypropyldicarbylmonoalkoxysilane, (meth) acryloyloxypropylmonocarbyldialkoxysilane and (meth) acryloyloxypropyldicarbyldialkoxysilane. ) When two or more acryloyloxypropyl trialkoxysilanes are selected and used, the proportion of these alkoxysilanes is selected according to the molecular structure of the desired (meth) acryloyloxyl-containing organopolysiloxane having a high degree of polymerization. You just have to do it and you are not restricted. Since the (meth) acryloyloxypropyl trialkoxysilane is trifunctional, the more the silane is used, the more branches in the molecule.

The alkoxysilanes of the above general formulas (1) and (2) are co-hydrolyzed and then polycondensed. However, the hydrolysis reaction and the subsequent polycondensation reaction proceed as distinct and distinct steps. Absent. A part of the silane having a silanol group generated by co-hydrolyzing the alkoxysilanes of the general formulas (1) and (2) is condensed at the same time as the formation, and the alkoxy group remaining at the stage of the polycondensation reaction still remains. This is because they undergo hydrolysis. Further, since the silane having a silanol group undergoes polycondensation simultaneously with its generation, the reaction product obtained by co-hydrolysis may be directly subjected to the next silylation step to have a molecular weight of 3,000 or more (GP
In some cases, the desired organopolysiloxane (in terms of polystyrene by C) can be obtained. However, in order to surely obtain such an organopolysiloxane, as in the present invention, the reaction product after co-hydrolysis may be used. Needs to be subjected to a silylation step after being subjected to polycondensation.

The co-hydrolysis in the present invention is generally carried out at 0 to
The reaction is carried out at 50 ° C. The following polycondensation is carried out in such a manner that the reaction product
The reaction is performed by further reacting at 0 ° C. as a result,
Almost no alkoxy groups remain in the obtained co-hydrolyzed polycondensate, but some silanol groups remain unreacted. In the production method of the present invention, the co-hydrolyzed polycondensate is subjected to the following silylation in order to prevent silanol groups from remaining in the (meth) acryloyloxyl group-containing organopolysiloxane which is the object of the present invention. Provide to the process.

(B) Step of Silylating Co-Hydrolysis Condensate In this step, the co-hydrolysis condensation polymer is reacted with a silylating agent to remove silanol groups remaining in the co-hydrolysis condensation polymer. To silylate. Examples of the silylating agent, for example, the general formula _{^{(3): R 6 3 Si}} -NH-SiR 6 3 (3) ( wherein, R ⁶ is independently an alkyl group) hexaalkyldisilazanes represented by Is mentioned. Examples of the alkyl group represented by R ⁶ in the general formula (3) include the aforementioned R ³
And the like.

Specific examples of the hexaalkyldisilazane represented by the general formula (3) include, for example, hexamethyldisilazane, tetramethyldibutyldisilazane, hexaethyldisilazane and the like. Is preferred. Examples of the silylating agent other than the hexaalkyldisilazane of the general formula (3) include N-
Trimethylsilylacetamide, N, O-bis (trimethylsilyl) acetamide, N-trimethylsilylimidazole and the like. Among the above silylating agents, preferred is hexaalkyldisilazane. This silylation reaction is usually performed in an organic solvent, and examples of such an organic solvent include methyl tributyl ketone, toluene, xylene and the like. By the silylation, the active hydrogen atom of the silanol group remaining in the co-hydrolyzed polycondensate is replaced with an inactive triorganosilyl group. That is, when the silylating agent is hexamethyldisilazane, the silanol group is converted to a trimethylsiloxy group.

The amount of the silylating agent to be used cannot be unconditionally determined by the amount of silanol groups remaining in the co-hydrolyzed polycondensation product. preferable. The temperature of the silylation reaction is 80
C. or higher, and the reaction time may be about 0.5 to 3 hours. By this silylation step, the silanol groups remaining in the co-hydrolyzed polycondensate are almost completely converted to triorganosiloxy groups and become inactive.

The (meth) acryloyloxyl group-containing organopolysiloxane obtained by subjecting the cohydrolyzed polycondensate to a silylation step as described above has an average molecular weight of usually 3,000 or more (polystyrene conversion by GPC). Value). When used as a base polymer of the above-mentioned electron beam curable resin composition, thermosetting resin composition, photocurable resin composition, etc., the average molecular weight is 3,000 to 100,
000 (polystyrene conversion value by GPC) is preferable, and the range of 5,000 to 50,000 (polystyrene conversion value by GPC) is more preferable, but those having such a molecular weight can be easily produced.

(Meth) obtained by the production method of the present invention
The acryloyloxyl group-containing organopolysiloxane can be easily purified by washing with water, and can be obtained as a high-purity solid state. Further, depending on the use, it can be used after being dissolved in an organic solvent such as toluene, xylene, methyl isobutyl ketone, and acetone.

[0021]

The present invention will be described more specifically below with reference to examples and comparative examples. In this example, the average molecular weight is G
It is a polystyrene conversion value by PC (gel permeation chromatography). Example 1 Acryloyloxypropyltrimethoxysilane 468
Parts by weight (2 mol) and phenyltrimethoxysilane 5
94 parts by weight (3 mol) were charged into a flask, and water 4
46 parts by weight (25 mol) and hydrochloric acid (3
(6%) A solution obtained by mixing 1.2 parts by weight was added dropwise to carry out hydrolysis. Next, the obtained reaction mixture is heated to 80 ° C., and polycondensation is carried out while distilling off by-produced methyl alcohol, and a reaction solution containing a co-hydrolyzed polycondensate having an average molecular weight (M _w ) of 15,000. I got After separating this co-hydrolyzed polycondensate from the reaction solution, it was dissolved in methyl isobutyl ketone, and 25 parts by weight of hexamethyldisilazane was added per 100 parts by weight of solids of the co-hydrolyzed polycondensate, and 1
Heated at 00 ° C. for 1 hour. Next, the obtained reaction mixture was subjected to a reduced pressure strip treatment at 100 ° C. and 5 mmHg to obtain a (meth) acryloyloxyl group-containing organopolysiloxane as a resinous solid.

The resulting (meth) acryloyloxyl group-containing organopolysiloxane has an average molecular weight (M _w ) of 1
4,500, the softening point is 55 ° C, and the yield is 90.
%Met. FIG. 2 shows an infrared analysis chart of the obtained co-hydrolyzed polycondensation product before silylation, and FIG. 1 shows an infrared analysis chart of the silylated (meth) acryloyloxyl group-containing organopolysiloxane of the present invention. .
In FIG. 2 , the absorption derived from the silanol group is 900 cm.
^-1 and around 3400-3500 cm ^-1 , but it can be seen in FIG. 1 that these absorptions have completely disappeared.

Example 2 A (meth) acryloyloxyl group-containing organopolysiloxane synthesized in the same manner as in Example 1 was dissolved in toluene so that the concentration of non-volatile components became 35% by weight, and 100 parts by weight of the obtained solution was obtained. With pure water (conductivity 1 μs / cm or less) 2
It was washed twice with 00 parts by weight. As a result, the conductivity of the first washing wastewater was 13 μs / cm, and the conductivity of the second washing wastewater was reduced to 4 μs / cm. It was then washed (meth) acrylate water azeotropically dehydrated toluene solution of Roy Luo hexyl group-containing organopolysiloxane, and further toluene was distilled off, the average molecular weight (M _W) 14,00
A (meth) acryloyloxyl group-containing organopolysiloxane having a softening point of 52 ° C. was obtained as a solid. Yield 8
8%.

COMPARATIVE EXAMPLE 1 The reaction components were subjected to co-hydrolysis, and the same procedure as in Example 1 was carried out until polycondensation.
_W ) A reaction solution containing 15,000 co-hydrolyzed polycondensates was obtained. Next, 2.4 parts by weight of propylene oxide was added to the reaction solution 1509.2 to neutralize the acid catalyst, and the mixture was stirred and subjected to a reduced pressure stripping treatment at 100 ° C./5 mmHg to obtain a co-hydrolyzed polycondensate as a resin solid. Obtained. Average molecular weight of the co-hydrolytic condensation polymerization product (M _W) is 15,500, a softening point is 60 ° C., the yield was 91%.

Comparative Example 2 A co-hydrolyzed polycondensate synthesized in the same manner as in Comparative Example 1 was dissolved in methyl isobutyl ketone so that the nonvolatile content was 35% by weight, and 100 parts by weight of the obtained solution was purified water ( It was washed twice with 200 parts by weight (conductivity: 1 μs / cm or less). As a result, the conductivity of the first washing wastewater was 10 μs / cm, and the conductivity of the second washing wastewater decreased to 3 μs / cm. However, when the organic phase and the aqueous phase were separated after washing. Because of the formation of an emulsion phase, separation was extremely difficult and accompanied by loss of the co-hydrolyzed polycondensate. Next, water was azeotropically dehydrated from the washed solution of the co-hydrolyzed polycondensate in methyl isobutyl ketone, and the methyl isobutyl ketone was distilled off to obtain the co-hydrolyzed polycondensate as a solid. Average molecular weight of the co-hydrolytic condensation polymerization product (M _W) is 14,500, a softening point is 52 ° C., the yield was 35%.

The following storage stability tests were conducted on the (meth) acryloyloxyl group-containing organopolysiloxane of the present invention obtained in Examples 1 and 2 and the cohydrolyzed polycondensate obtained in Comparative Examples 1 and 2. The purity was evaluated based on the measurement of the amount of free chlor and the amount of hydrolyzable chlor. Table 1 shows the results.

Storage stability test The (meth) acryloyloxyl group-containing organopolysiloxanes obtained in Examples 1 and 2 or the co-hydrolyzed polycondensate obtained in Comparative Examples 1 and 2 were mixed with methyl isobutyl ketone to obtain a nonvolatile component. It dissolved so that a density | concentration might be set to 45 weight%.
The initial viscosities at 25 ° C. of the obtained solutions were as shown in Table 1, respectively. In addition, these solutions were
Was allowed to stand for 1 day to a maximum of 75 days to measure the change over time in viscosity. Table 1 also shows the results. In addition, "gelation" in the table
Indicates that the solution gelled and the viscosity could not be measured.

Evaluation of Purity (Measurement of Free Chlorine Amount) Organopolysiloxane containing (meth) acryloyloxyl group obtained in Examples 1 and 2 or co-hydrolyzed polycondensate 1 obtained in Comparative Examples 1 and 2
0.0 g of acetone / methanol mixed solution (2: 1) 6
0 ml, and add this solution to a magnetic stirrer for 3 minutes.
After stirring for 0 minutes, 3 drops of a BTB solution were added as an indicator. Next, nitric acid was added until the solution turned yellow, and 3 drops of the above indicator were added. The solution was subjected to potentiometric titration with an aqueous solution of silver nitrate using an automatic titrator (using a silver electrode) to determine the amount of free chlor.

(Amount of hydrolyzable chlor) In the above measurement of the amount of free chlor, 60 ml of an acetone / methanol mixed solution (2: 1) was added. ₃ O
Except for adding 2 g of a 28 wt% methanol solution of Na,
Potentiometric titration was performed in the same manner as in the measurement of the amount of free chlor to determine the amount of hydrolyzable chlor.

[0030]

[Table 1]

[0031]

According to the present invention, a solid having excellent storage stability is provided.
A (meth) acryloyloxyl group-containing organopolysiloxane in a shape can be obtained by a simple process with a high yield. Further, the obtained (meth) acryloyloxyl group-containing organopolysiloxane is easily removed from water-soluble impurities by washing with water in an organic solvent immiscible with water such as toluene, xylene, etc. It can be purified.

[Brief description of the drawings]

FIG. 1 is an infrared analysis chart of a (meth) acryloyloxyl group-containing organopolysiloxane of the present invention obtained in Example 1.

FIG. 2 is an infrared analysis chart of the co-hydrolyzed polycondensate obtained in Example 1 before the silylation treatment.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Shinsuke Yamaguchi 1-10 Hitomi, Matsuida-cho, Usui-gun, Gunma Prefecture Shin-Etsu Chemical Co., Ltd. Silicone Electronics Materials Research Laboratory (56) References JP-A-6-32903 ( JP, A) JP-A-62-275132 (JP, A) JP-A-6-329804 (JP, A)

Claims (3)

(57) [Claims] 1. A (A) represented by the following general formula _{(1): CH 2 = CR} 1 COO-C 3 H 6 -SiR 2 a (OR 3) 3-a (1) ( wherein, R ¹ represents a hydrogen atom or A methyl group, R ² is an unsubstituted or substituted monovalent hydrocarbon group, R ³ is an alkyl group, and a is an integer of 0 to 2). And the following general formula (2): R ⁴ _4-n Si (OR ⁵ ) _n (2) (wherein, R ⁴ is an unsubstituted or substituted monovalent hydrocarbon group, and R ⁵ is an alkyl group. , N is an integer of 1 to 4) in the presence of hydrochloric acid , followed by co-hydrolysis, followed by polycondensation to obtain a co-hydrolyzed condensate having a silanol group, and (B Reacting the co-hydrolyzed polycondensate with a silylating agent to silylate the silanol groups. The amount more than 3,000-solid (meth) acryloyl Luo manufacturing method of hexyl group-containing organopolysiloxane (in terms of polystyrene by GPC). 2. The method for producing a solid (meth) acryloyloxyl group-containing organopolysiloxane according to claim 1, wherein the silylating agent is a hexaalkyldisilazane. 3. After the step (B) for silylation, the obtained
Solid (meth) acryloyloxyl group-containing or
Dissolve ganopolysiloxane in water-immiscible organic solvent
To remove water-soluble impurities by washing with water
The solid (meth) acrylic according to claim 1, which has a process.
Method for producing organopolysiloxane containing loyloxyl group
Law.