JPH04227949A - Production of resin composition having phenolic hydroxyl group - Google Patents

Abstract

PURPOSE:To obtain a resin composition prevented from decreasing in flow, mechanical strengths, etc., with time by subjecting a specified organopolysiloxane to a crosslinking reaction in the presence of an emulsifier, a crosslinking agent, a catalyst and water in a resin having phenolic hydroxyl groups. CONSTITUTION:An organopolysiloxane having silanol groups at both terminals is mixed with an emulsifier comprising a compound of formula I (wherein R' and R'' are each 2-5C hydrocarbyl, POA is polyoxyalkylene comprising an adduct of EO with PO; (x) is 200-990; (y+z)=10-800, and (x+y+z)<0) or a compound of formula II (wherein R is 4-12C alkyl, (n) is 1-20; EO is ethylene oxide; PO is propylene oxide; (x) and (y) are each 0-100; and 5<=x+y<=100), a crosslinking agent and a catalyst to obtain a mixture. The mixture is reacted in a molten resin having phenolic hydroxyl groups while water is continuously or intermittently added to the reaction system, and water is removed after the reaction.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention relates to a resin having phenolic hydroxyl groups (hereinafter referred to as
The present invention relates to a novel method for producing a composition (abbreviated as phenolic resin).

0002

[Prior Art] Phenolic resin has relatively good curability and moldability, and its cured product has excellent electrical and mechanical properties, making it a well-balanced material for molding materials, laminated materials, and brake linings. Friction materials, shell molds, etc.
It is widely used in cast materials, foam materials, etc., and is an industrially valuable material.

However, since phenolic resins are inherently brittle, when used as molded materials or laminated materials, they tend to crack due to rapid temperature changes such as repeated cold and hot temperatures. Furthermore, when producing a molded body with a metal insert, cracks may occur at the contact surface between the metal and the phenolic resin after molding, resulting in a decrease in production yield.

[0004] Also, when used as a friction material for brake linings, etc., or as a binding material for shell mold materials,
Since phenolic resin is hard and brittle, cracks, chips, etc. may occur.

[0005] In order to improve these drawbacks of phenolic resins, a method of mixing phenolic resins with nitrile rubber or acrylic polymers has been proposed.

However, since nitrile rubber and acrylic polymers inherently have lower heat resistance than phenolic resins,
When a molded article or a laminate made of a phenolic resin obtained by the above method is continuously used under severe temperature conditions, for example, at a high temperature of 200° C. or higher, the mechanical strength may decrease. Furthermore, when used as a friction material, there are restrictions in terms of use, such as a decrease in the coefficient of friction at high temperatures.

[0007] As a method to solve such problems,
For example, in JP-A-63-251452 and JP-A-1-230661, silicone is added as microparticles in resin in order to improve mechanical strength, crack resistance, thermal shock resistance, heat deterioration resistance, etc. Dispersed phenolic resin compositions have been proposed.

However, the silicone rubber dispersed in the phenolic resin composition disclosed in these documents has a large particle size and the crosslinking reaction has not progressed sufficiently, so that the effect of improving the above-mentioned physical properties is insufficient.

Specifically, if silicone rubber is insufficiently crosslinked in a phenolic resin, uncrosslinked silicone will separate and precipitate on the resin surface, and in the case of a liquid phenolic resin composition, the viscosity and fluidity will decrease. In addition, in the case of solid phenolic resins, the flow characteristics, which are the curing characteristics of the resin, deteriorate over time, and the mechanical strength, crack resistance, thermal shock resistance, heat deterioration resistance, etc. deteriorate over time. This is a problem.

0010

OBJECTS OF THE INVENTION The purpose of the present invention is to solve the above-mentioned problems and to solve the problem of over time deterioration of flow characteristics and deterioration of mechanical strength, crack resistance, thermal shock resistance, heat deterioration resistance, etc. over time. An object of the present invention is to provide a method for producing a phenolic resin composition free of phenolic resins.

[0011]

[Means for Solving the Problem] As a result of intensive studies to achieve the above object, the present inventors have achieved the above object by dispersing silicone rubber in which the crosslinking reaction has sufficiently progressed in the form of fine particles in a phenolic resin. The inventors discovered that the problem could be solved and arrived at the present invention.

That is, the present invention adds an emulsifier, an organopolysiloxane having silanol groups at both ends of the molecule, a crosslinking agent for silanol condensation, and a catalyst for silanol condensation to a heated and melted resin having phenolic hydroxyl groups. A phenolic hydroxyl group characterized in that water is continuously or intermittently charged into the mixed mixture, a crosslinking reaction of the organopolysiloxane is carried out in the resin having a phenolic hydroxyl group, and water is removed after the reaction is completed. A method for producing a resin composition having the following.

A feature of the present invention is that a specific silicone compound is subjected to a crosslinking reaction in a resin having a phenolic hydroxyl group in the presence of a specific emulsifier, a crosslinking agent, and a catalyst in the presence of water, and the obtained silicone rubber is The purpose is to disperse the resin as fine particles in a resin having phenolic hydroxyl groups.

The present invention will be explained in detail below.

The resin having a phenolic hydroxyl group (hereinafter abbreviated as phenolic resin) used in the present invention is:
Phenols such as phenol, cresol, xylenol, resorcinol, bisphenol A, paratertiary butylphenol, paraoctylphenol, α-
Compounds having one or more phenolic hydroxyl groups selected from the group consisting of naphthols such as naphthol and β-naphthol (hereinafter referred to as phenolic compounds) and aldehydes such as formaldehyde, paraformaldehyde and trioxane There are novolac resins obtained by reacting aldehydes such as phenolic compounds using an acidic catalyst, and resol resins obtained by reacting the above phenolic compounds with aldehydes using an alkaline catalyst. A phenolic aralkyl resin derived from a phenolic compound and a paraxylylene dihalide such as paraxylene dichloride or a paraxylylene dialkyl ether such as paraxylylene dimethyl ether (for example, trade name "Milex XL-225" manufactured by Mitsui Toatsu Chemical Co., Ltd.) ), naphthol aralkyl resin, etc.

[0016] These phenolic resins are not subject to any restrictions in producing the phenolic resin composition of the present invention, and may be used alone or in combination of two or more.

The emulsifier used in the present invention has the general formula (1) [
5]

[0018]

[Formula 5] (wherein R', R'' are the same or different C2 to C5 divalent hydrocarbon groups, POA is ethylene oxide and/or
or a polyoxyalkylene group consisting of an adduct of propylene oxide, x is an integer from 200 to 990, y+z=1
A modified silicone oil having an epoxy group and/or a polyoxyalkylene group in the side chain represented by 0 to 800 and x+y+z<1000 is used.

There are no particular restrictions on the molecular weight of the modified silicone used as the emulsifier, that is, the values of x, y, and z in the above general formula (1), or the chain length of the polyoxyalkylene group, but the value of z ( As the number of polyoxyalkylene groups (number of polyoxyalkylene groups) increases and the chain length increases, the compatibility of the organopolysiloxane, which has silanol groups at both ends of the molecule, with the phenolic resin increases, and the dispersed particle size of the silicone contained in the resin becomes microscopic. Furthermore, when the value of z is decreased and the chain length is shortened, the compatibility tends to decrease.

That is, by appropriately selecting the values of x, y, and z, it is possible to control the particle size of the silicone rubber dispersed in the phenolic resin within the range of 0.1 to 10 μm.

Other emulsifiers used in the present invention are:
General formula (2) [Chemical formula 6]

[0022]

[Formula 6] (wherein, R is a C4-C12 alkyl group, n is 1 on average
An integer of ~20, EO indicates that ethylene oxide is added, PO indicates that propylene oxide is added, x and y are integers of 0 to 100, and 5≦x+y≦100
An adduct of an alkylphenol-formalin condensate represented by ethylene oxide and/or propylene oxide is used.

R in the above general formula (2) is preferably a C4 to C12 alkyl group such as a butyl group, hexyl group, nonyl group, or dodecyl group. When R is C3 or less, it becomes difficult to control the dispersed particle size of the silicone rubber dispersed in the phenolic resin, and when R is C13 or more, it becomes difficult to obtain alkylphenol, which is not economical. n is 1 on average
~20, that is, the average number of nuclei ranges from 3 to 22. In this case as well, if n is less than 1 on average, it will be difficult to control the dispersed particle size of the silicone rubber. When n is 21 or more on average, it becomes difficult to synthesize an alkylphenol-formalin condensate.

In addition, the number of moles of adducts of ethylene oxide and propylene oxide is expressed as the number of moles of ethylene oxide x,
When the number of moles of propylene oxide is y (each average), the total of x and y is 5 to 100, and x may be 0 or y may be 0.

By appropriately selecting the adducts x and y of ethylene oxide and/or propylene oxide of the alkylphenol-formalin condensate used as the emulsifier, that is, the number of moles of ethylene oxide added and the number of moles of propylene oxide added, The silicone rubber in the phenolic resin can be controlled as microparticles in the range of 0.1 to 10 μm.

The amount of these emulsifiers added is preferably 0.01 to 25 parts by weight per 100 parts by weight of the phenolic resin. If it is less than 0.01 part by weight, it becomes difficult to control the dispersed particle size of the silicone rubber in the phenolic resin within the range of 0.1 to 10 μm. Moreover, if it exceeds 25 parts by weight, the cost will increase, which is not preferable.

The organopolysiloxane having silanol groups at both ends of the molecule used in the present invention has the general formula (3
) [C7]

[0028]

[Formula 7] (wherein R1 and R2 are the same or different monovalent hydrocarbon groups, alkyl groups such as methyl, ethyl, propyl, butyl, aryl groups such as phenyl and xylyl, γ
- represents a halogenated monovalent hydrocarbon group such as a chloropropyl group or a 3,3,3-trifluoropropyl group).

The silanol groups of organopolysiloxane having silanol groups at both ends of the molecule have a hydroxyl equivalent of 5
00 to 200,000 is preferable, and if it is less than 500, a phenolic resin composition having crack resistance and thermal shock resistance cannot be obtained. On the other hand, if it exceeds 200,000, it becomes difficult to control the dispersed particle size of the silicone rubber.

[0030] Organopolysiloxane having silanol groups at both ends of the molecule is a phenolic resin 100
It is preferable to add 3 to 50 parts by weight based on the weight part. If it is less than 3 parts by weight, it will not be effective in improving the crack resistance or thermal shock resistance of the resulting phenolic resin composition, and if it exceeds 50 parts by weight, the mechanical strength etc. will decrease, which is not preferable.

The crosslinking agent for silanol condensation used in the present invention has three or more functional groups such as an alkoxy group, an acyloxy group, a ketoxime group, an alkenyloxy group, an aminooxy group, an amino group, and a hydrogen group directly bonded to a silicon atom. These are polyfunctional silanes and polyfunctional polysiloxanes.

Examples of polyfunctional silanes include methyltrimethoxysilane, vinyltrimethoxysilane, 3-
Alkoxysilanes such as chloropropyltrimethoxysilane, 3-aminopropyltriethoxysilane, vinyltriethoxysilane, methyltriethoxysilane, ketooxime silanes such as methyltris(dimethyloxime)silane, methyltris(methylethylketoxime)silane, vinyltriacetoxy Silane, acyloxysilane such as methyltriacetoxysilane, alkenyloxysilane such as vinyltripropenyloxysilane, methyltriisobutenylsilane, aminooxysilane such as methyltris(N,N-diamylaminooxy)silane, vinyltris(N- Examples include aminosilanes such as butylamino)silane.

[0033] Furthermore, as polyfunctional polysiloxanes,
General formula (4) [Chemical formula 8]

[0034]

Examples include methylhydrogenpolysiloxane represented by the following formula (wherein n is an integer of 3 to 10,000).

These silanol condensation crosslinking agents are preferably added in an amount of 0.05 to 5 parts by weight per 100 parts by weight of the phenolic resin. If it is less than 0.05 parts by weight, crosslinking of the silicone rubber will be insufficient, and it will not be effective in improving the crack resistance or thermal shock resistance of the phenolic resin composition. If it exceeds 5 parts by weight, the cost will increase, which is not preferable. The above-mentioned crosslinking agents for silanol condensation can be used alone or in combination of two or more.

The silanol condensation catalyst used in the present invention includes organic tin compounds such as dibutyltin dilaurate, dibutyltin diacetate, tin oleate, and tin naphthenate, which have been conventionally used to produce silicone rubber. Can be mentioned.

These silanol condensation catalysts are organopolysiloxanes having silanol groups at both ends of the molecule.
It is preferable to add 5 parts by weight or less per 00 parts by weight. Exceeding this is not preferable as it increases the cost.

The above organotin compound is a relatively unstable compound and is easily hydrolyzed by water. The hydrolyzate then becomes the true catalyst for silicone rubber. Therefore, in order to sufficiently proceed with the crosslinking reaction of silicone rubber, it is essential to charge water into the reaction system.

That is, to the heated and melted phenolic resin, (1) an emulsifier is added, (2) an organopolysiloxane having silanol groups at both ends of the molecule, (2) a crosslinking agent for silanol condensation, and (2) a catalyst for silanol condensation. After thorough mixing, water is continuously or intermittently charged to this mixture to proceed with the crosslinking reaction of the silicone rubber in the phenolic resin.

Although the water used may contain impurities, it is preferably clarified water, distilled water, clean water, ionized water, or steam from which impurities have been removed as much as possible. It is necessary to add 0.1 to 100 parts by weight of this water to 100 parts by weight of the phenolic resin. If it is less than 0.1 part by weight, the crosslinking reaction of the silicone rubber, which is a feature of the present invention, will not proceed sufficiently, and if it exceeds 100 parts by weight, the dehydration step after the reaction will be difficult and undesirable, and bumping, steam explosion, etc. may occur. It is easy and dangerous.

Therefore, this water should be added in an amount of 0.1 to 100 parts by weight to 1 to 15 parts by weight per 100 parts by weight of the phenolic resin.
It is preferable to add it continuously or intermittently over time.

In addition, the effect of charging this water is that in addition to activating the catalyst for silanol condensation of silicone rubber, the low-molecular condensate generated by the condensation reaction is entrained by water and remains outside the reaction system. It has the advantage of being able to be removed. Therefore, it is thought that the crosslinking reaction of the silicone rubber progresses even further.

[0043] Specifically, the method for producing the phenolic resin composition of the present invention involves heating and melting 100 parts by weight of a phenolic resin at 60 to 200°C in the presence or absence of a solvent. After that, 0.01 to 25 parts by weight of emulsifier (1) is added while stirring and thoroughly mixed.

[0044] At this time, the emulsifier used has the values of x, y, and z in the general formula (1) above, or
Select the values of x and y in the general formula (2). Next, ■
3 to 50 parts by weight of an organopolysiloxane having silanol groups at both ends of the molecule, 0.
05 to 5 parts by weight, ■Organopolysiloxane 10 having silanol groups at both ends of the molecule as a catalyst for silanol condensation
Add 5 parts by weight or less to 0 parts by weight and mix well, then add 0.1 to 100 parts by weight of water to 100 parts by weight of the phenolic resin continuously or intermittently over 1 to 15 hours. , a crosslinking reaction of silicone rubber is carried out in a phenolic resin at 60 to 200°C.

The method for adding these components is as follows: (1) an organopolysiloxane having silanol groups at both ends of the molecule, (2) a crosslinking agent for silanol condensation, and (2) a catalyst for silanol condensation, which are uniformly mixed all at once and added. This is not preferable because the crosslinking reaction proceeds during the addition. It is preferable to separate and add at least one component among each component.

[0046] After each component forming the silicone rubber is added to the phenolic resin, a crosslinking reaction of the silicone rubber is carried out in the phenolic resin while continuously or intermittently charging water to this mixture. After the reaction is completed, unnecessary water in the system is dehydrated under normal pressure or reduced pressure to obtain a phenolic resin composition.

The dispersed particle size of the silicone rubber in the phenolic resin composition thus produced can be easily observed using an electron microscope or an optical microscope.

According to the present invention, the crosslinking reaction of the silicone rubber can proceed sufficiently in the phenolic resin, and furthermore, the rubber can be uniformly dispersed in the phenolic resin as fine particles.

Therefore, the phenolic resin composition obtained by the production method of the present invention has excellent mechanical strength, which is a characteristic of phenolic resin materials, and also has the crack resistance and heat deterioration resistance that silicone rubber has. It also has Furthermore, these properties and moldability do not deteriorate over time.

[0050]

[Examples] The present invention will now be explained in more detail with reference to Examples and Test Examples. "Parts" in each example represent "parts by weight."

[0051] The emulsifier represented by general formula (2) is
Various phenols were formalin-crosslinked under a sulfuric acid catalyst using a conventional method, and the average value of n in the formula was calculated from the average number of nuclei determined by gel permeation chromatography (hereinafter referred to as GPC) analysis. , ethylene oxide, and propylene oxide were prepared at high temperature and under pressure to form the desired emulsifier.

Example 1 100 parts of a phenol novolac resin (manufactured by Mitsui Toatsu Chemical Co., Ltd., Novolac #2000) was heated and melted at a temperature of 170°C. Next, while stirring this, a modified silicone oil (Toray, Dow Corning, 3 parts of Silicone Co., Ltd. (trade name: SF8421) were added and stirred for 30 minutes.

Next, represented by the general formula (3), R1, R2
10 parts of an organopolysiloxane having a silanol group at both ends of a molecule having a hydroxyl equivalent of 2000, in which is a methyl group, was added, stirring was continued for 1 hour, and further 0.25 part of methyltrimethoxysilane and 0.2 parts of dibutyltin diacetate were added. 02 parts of the mixture was added and stirred for 30 minutes.

Next, water was added to this mixture at a rate of 2.4 parts/hr per 100 parts of the phenol novolac resin, and the silicone rubber was heated at 170° C. for 5 hours while distilling the generated condensate etc. out of the system. After the crosslinking reaction, unnecessary water remaining in the system was removed by dehydration under reduced pressure to obtain a phenolic resin composition in which the average dispersed particle size of silicone rubber was 10 μm.

Example 2 100 parts of a phenol aralkyl resin (manufactured by Mitsui Toatsu Chemical Co., Ltd., trade name: Mirex XL-225) was heated and melted at a temperature of 170°C. Next, while stirring this, a modified silicone oil (manufactured by Toray Dow Corning Silicone Co., Ltd., trade name: SF8410), which is represented by the general formula (1) and has only POA groups and has a viscosity of 2900 centistokes at 25°C, is added. 10 parts were added and stirred for 30 minutes.

Next, represented by the general formula (3), R1, R2
20 parts of an organopolysiloxane having a silanol group at both ends of a molecule having a hydroxyl equivalent of 4000, in which is a methyl group, and 0.0 parts of a methylhydrogenpolysiloxane represented by the general formula (4) and having a viscosity of 30 centistokes at 25°C.
2 parts of the mixture was added and stirring was continued for 2 hours, and further 0.15 part of dibutyltin dilaurate was added and stirred for 30 minutes.

Next, steam was added to this mixture at a rate of 6.3 parts/hr per 100 parts of the phenol aralkyl resin, and the crosslinking reaction of the silicone rubber was carried out at 170° C. for 2 hours while distilling the generated condensate etc. out of the system. After performing this, unnecessary water remaining in the system was removed by dehydration under reduced pressure to obtain a phenolic resin composition in which the average dispersed particle size of silicone rubber was 0.1 μm.

Example 3 100 parts of a phenol novolac resin (manufactured by Mitsui Toatsu Chemical Co., Ltd., trade name: Novolac #2000) was heated and melted at a temperature of 170°C. Next, while stirring, a modified silicone oil (Toray Dow Corning Silicone Co., Ltd. manufactured by, product name: SF8411) 0
．． 5 parts were added and stirred for 30 minutes.

Next, represented by the general formula (3), R1, R2
10 parts of an organopolysiloxane having a silanol group at both ends of a molecule with a hydroxyl equivalent of 1,500 and a methyl group are added, stirring is continued for 1 hour, and 1.25 parts of tetra(n-propoxy)silane and dibutyltindi are added. Acetate 0.
Added 25 parts of the mixture and stirred for 30 minutes.

Next, water was added to this mixture at a rate of 3.13 parts/hr based on 100 parts of the phenol novolak resin, and the silicone rubber was crosslinked at 170° C. for 2 hours while distilling the generated condensate etc. out of the system. After the reaction, unnecessary water remaining in the system was removed by dehydration under reduced pressure to obtain a phenolic resin composition in which the average dispersed particle size of silicone rubber was 8 μm.

Example 4 Phenol resol resin (manufactured by Gunei Chemical Co., Ltd., trade name:
Add 120 parts of acetone to 100 parts of PS-4104) and add 6
It was heated and melted at a temperature of 0°C. Next, while stirring this, a modified silicone oil (manufactured by Toray Dow Corning Silicone Co., Ltd., trade name: SH3771) expressed by the general formula (1), having a POA group, and having a viscosity of 320 centistokes at 25° C. of the mixture was added and stirred for 30 minutes.

Next, represented by the general formula (3), R1, R2
30 parts of an organopolysiloxane having a silanol group at both ends of a molecule with a hydroxyl equivalent of 5,000, in which is a methyl group, was added, stirring was continued for 2 hours, and further 0.2 part of γ-aminopropyltrimethoxysilane and 0 part of dibutyltin dioctanoate were added. 0.02 parts of the mixture was added and stirred for 30 minutes.

Next, water was added to this mixture at a rate of 2.4 parts/hr per 100 parts of the phenol resol resin, and the silicone rubber was crosslinked at 60° C. for 2 hours while distilling the generated condensate etc. out of the system. After the reaction, unnecessary moisture remaining in the system was removed by dehydration under normal pressure to obtain a phenolic resin composition in which the average dispersed particle size of silicone rubber was 1 μm.

Example 5 100 parts of a phenol novolac resin (manufactured by Mitsui Toatsu Chemical Co., Ltd., trade name: Novolac #2000) was heated and melted at a temperature of 170°C. Next, while stirring this, 2 parts of an emulsifier prepared by adding an average of 10.5 moles of ethylene oxide per active hydrogen to a para-secondary butylphenol-formalin condensate represented by the general formula (2) where R is C4 is added, and the mixture is stirred for 30 minutes. I did it.

Next, represented by the general formula (3), R1, R2
10 parts of an organopolysiloxane having a silanol group at both ends of a molecule with a hydroxyl equivalent of 2000, in which is a methyl group, was added, stirring was continued for 1 hour, and further 0.2 parts of methyltrimethoxysilane and 0.2 parts of dibutyltin diacetate were added. 01 part of the mixture was added and stirred for 30 minutes.

Next, water was added to this mixture at a rate of 5.2 parts/hr per 100 parts of the phenol novolac resin, and the silicone rubber was crosslinked at 170° C. for 12 hours while distilling the generated condensate etc. out of the system. After the reaction, unnecessary moisture remaining in the system was removed by dehydration under reduced pressure to obtain a phenolic resin composition in which the average dispersed particle size of silicone rubber was 10 μm.

Example 6 100 parts of a phenol aralkyl resin (manufactured by Mitsui Toatsu Chemical Co., Ltd., trade name: Mirex XL-225) was heated and melted at a temperature of 170°C. Next, while stirring, the formula (2) is expressed, R is a C9 nonyl group, and n is 2.
To the nonylphenol-formalin condensate was added 3 parts of an emulsifier containing 31.5 moles of ethylene oxide on average per active hydrogen, and the mixture was stirred for 30 minutes.

Next, represented by the general formula (3), R1, R2
20 parts of an organopolysiloxane having silanol groups at both ends of a molecule having a hydroxyl equivalent of 5,000, in which is a methyl group, and 0.0 parts of a methylhydrogenpolysiloxane represented by the general formula (4) and having a viscosity of 30 centistokes at 25°C.
3 parts of the mixture was added and stirring was continued for 2 hours, and further 0.1 part of dibutyltin dilaurate was added and stirred for 30 minutes.

Next, water was added to this mixture at a rate of 1.33 parts/hr based on 100 parts of the phenol aralkyl resin, and the silicone rubber was crosslinked at 170° C. for 2 hours while distilling the generated condensate etc. out of the system. After the reaction, unnecessary water remaining in the system was removed by dehydration under reduced pressure to obtain a phenolic resin composition in which the average dispersed particle size of silicone rubber was 6 μm.

Example 7 100 parts of a phenol aralkyl resin (manufactured by Mitsui Toatsu Chemical Co., Ltd., trade name: Mirex XL-225) was heated and melted at a temperature of 170°C. Next, while stirring this, emulsifier 5 is prepared by adding ethylene oxide to a nonylphenol-formalin condensate represented by the general formula (2), in which R is a C9 nonyl group, and n is 8, on average 60 moles per active hydrogen. of the mixture and stirred for 30 minutes.

Next, represented by the general formula (3), R1, R2
A mixture of 30 parts of an organopolysiloxane having silanol groups at both ends and 1 part of tetra(n-propoxy)silane is added to a molecule having a hydroxyl equivalent of 1500, in which is a methyl group,
Continue stirring for 1 hour, and add 0.0 dibutyltin dilaurate.
2 parts were added and stirred for 30 minutes.

Next, water was added to this mixture at a rate of 2.44 parts/hr based on 100 parts of the phenol aralkyl resin, and the silicone rubber was crosslinked at 170° C. for 3 hours while distilling the generated condensate etc. out of the system. After the reaction, unnecessary water remaining in the system was removed by dehydration under reduced pressure to obtain a phenolic resin composition in which the average dispersed particle size of silicone rubber was 0.1 μm.

Example 8 100 parts of a phenol novolac resin (manufactured by Mitsui Toatsu Chemical Co., Ltd., trade name: Novolac #2000) was heated and melted at a temperature of 170°C. Next, while stirring, it is expressed by the general formula (2), R is a C12 dodecyl group, and n
To a dodecylphenol-formalin condensate having a concentration of 8, 0.3 part of an emulsifier containing an average of 40 moles of ethylene oxide and an average of 20 moles of propylene oxide per active hydrogen group was added and stirred for 30 minutes.

Next, expressed by the general formula (3), R1, R2
5 parts of an organopolysiloxane having a silanol group at both ends of a molecule having a hydroxyl equivalent of 8,000 and which is a methyl group are added, and methyl hydrogen represented by the general formula (4) and having a viscosity of 30 centistokes at 25° C. 5 parts polysiloxane and 0.01 parts dibutyltin dioctanoate
The mixture was stirred for 30 minutes.

Next, water was added to this mixture at a rate of 0.9 parts/hr per 100 parts of the phenol novolac resin, and the silicone rubber was crosslinked at 170° C. for 5 hours while distilling the generated condensate etc. out of the system. After the reaction, unnecessary water remaining in the system was removed by dehydration under reduced pressure to obtain a phenolic resin composition in which the average dispersed particle size of silicone rubber was 0.4 μm.

Example 9 Naphthol aralkyl resin obtained from α-naphthol and paraxylylene dimethyl ether (softening point 105°C)
100 parts were heated and melted at a temperature of 170°C. next,
While stirring this, it is expressed by the general formula (1), has both an epoxy group and a POA group, and has a viscosity of 350°C at 25°C.
Two parts of modified silicone oil (manufactured by Dow Corning Toray Silicone Co., Ltd., trade name: SF8421) having an epoxy group equivalent weight of 6400 and 0 centistoke was added and stirred for 30 minutes.

Next, expressed by the general formula (3), R1, R2
10 parts of an organopolysiloxane having a silanol group at both ends of a molecule having a hydroxyl equivalent of 2000, in which is a methyl group, was added, stirring was continued for 1 hour, and further 0.25 part of methyltrimethoxysilane and 0.2 parts of dibutyltin diacetate were added. 02 parts of the mixture was added and stirred for 30 minutes.

Next, 2.0 parts/hr of water was added to this mixture based on 100 parts of the phenolic aralkyl resin.
After crosslinking the silicone rubber at 170°C for 5 hours while distilling the generated condensates out of the system, unnecessary water remaining in the system was removed by vacuum dehydration, and the average dispersed particle size of the silicone rubber was A phenolic resin composition having a thickness of 10 μm was obtained.

Comparative Example 1 100 parts of phenol novolac (manufactured by Mitsui Toatsu Chemical Co., Ltd., trade name: Novolac #2000) was heated and melted at a temperature of 170°C. Next, while stirring this, the general formula (
1), which has both an epoxy group and a POA group, and has 25
Modified silicone oil with a viscosity of 3500 centistokes at ℃ and an epoxy group equivalent of 6400 (manufactured by Toray Dow Corning Silicone Co., Ltd., trade name: SF8421)
) was added and stirred for 30 minutes.

Next, represented by the general formula (3), R1, R2
10 parts of an organopolysiloxane having a silanol group at both ends of a molecule having a hydroxyl equivalent of 2000, in which is a methyl group, was added, stirring was continued for 1 hour, and further 0.25 part of methyltrimethoxysilane and 0.2 parts of dibutyltin diacetate were added. A crosslinking reaction of the silicone rubber was carried out at 170° C. for 5 hours under stirring to obtain a phenolic resin composition in which the average dispersed particle size of the silicone rubber was 10 μm.

Comparative Example 2 100 parts of a phenol aralkyl resin (manufactured by Mitsui Toatsu Chemical Co., Ltd., trade name: Mirex XL-225) was heated and melted at a temperature of 170°C. Next, while stirring this, a modified silicone oil (manufactured by Toray Dow Corning Silicone Co., Ltd., trade name: SF8410), which is represented by the general formula (1) and has only POA groups and has a viscosity of 2900 centistokes at 25°C, is added. 10 parts were added and stirred for 30 minutes.

Next, represented by the general formula (3), R1, R2
20 parts of an organopolysiloxane having a silanol group at both ends of a molecule having a hydroxyl equivalent of 4000, in which is a methyl group, and 0.0 parts of a methylhydrogenpolysiloxane represented by the general formula (4) and having a viscosity of 30 centistokes at 25°C.
2 parts of the mixture was added, stirring was continued for 2 hours, and further, 0.15 part of dibutyltin dilaurate was added and a crosslinking reaction of the silicone rubber was carried out at 170°C for 2 hours with stirring, so that the average dispersed particle size of the silicone rubber was 0. A phenolic resin composition having a thickness of 1 μm was obtained.

Comparative Example 3 A phenolic resin composition was obtained in the same manner as in Example 1, except that the emulsifier represented by formula (1) and water were not used. The average dispersed particle size of the silicone rubber dispersed in the composition was 30 μm.

Test Example 1 10 parts of hexamine was added to 100 parts of each of the phenolic resin compositions obtained in Examples 1 to 3, 5 to 9 and Comparative Examples 1 to 3 and mixed by pulverization, and Example 4 After pulverizing the phenolic resin composition obtained in step 1 and leaving it at room temperature for the time shown in [Table 1],
Changes in flowability over time were evaluated by the method specified in 6910.

[0085] Almost no change over time in the flowability of the phenolic resin compositions obtained in each example was observed, indicating that the moldability was stable over time. The obtained results are shown in [Table 1].

[0086]

[Table 1]

Test Example 2 12 parts of hexamine, 120 parts of glass fiber, 60 parts of clay, and stearin were added to 100 parts of each of the phenolic resin compositions obtained in Examples 1 to 3, 5 to 9, and Comparative Examples 1 to 3. Add 2 parts of acid and 3 parts of carbon black to 110
After kneading for 3 minutes with heated rolls at ~120°C, the mixture was pulverized to form a molded powder. Next, a molded powder was obtained in the same manner as above except that hexamine was not added to 100 parts of the phenolic resin composition obtained in Example 4.

Each of these molded powders was divided into two parts, and one part was immediately subjected to the following test, and the other part was subjected to the following test after 180 days had passed.

[0089] Each molding powder was heated to a temperature of 170°C using a compression molding machine.
The molded product was compressed for 10 minutes at a pressure of 100 Kg/cm2 by Co., Ltd. and subjected to the following evaluation tests.

(1) Charpy impact test (JIS
K6911) (2) Bending test (JIS K6911) (3)
Thermal shock resistance test is conducted using the following method.

[0091] The base is a square with a side of 30 mm and a thickness of 5 mm.
Diameter 60mm, thickness 10mm with iron panel inserted
A molded article with a diameter of mm was prepared, and this molded article was left in a constant temperature dryer at 400° C. for 30 minutes, and then immersed in water for 10 minutes. This operation was considered as one cycle, and the number of cycles until cracking occurred was investigated.

As a result of each evaluation test, no deterioration over time was observed in any of the properties of the molded articles prepared from the phenolic resin compositions obtained in each example. The obtained results are shown in [Table 2].

[0093]

[Table 2]

[0094]

Effects of the Invention The phenolic resin composition obtained by the present invention shows no change in moldability over time. Moreover, the impact resistance, bending strength and thermal shock resistance (
The heat cracking resistance) is also stable with no deterioration over time.

Therefore, the phenolic resin composition can be used as various molding materials or friction materials that require excellent mechanical strength, crack resistance, thermal shock resistance, stress relaxation properties, or friction resistance. It is extremely useful industrially.

Claims (11)

[Claims] Claim 1: A mixture obtained by adding an emulsifier, an organopolysiloxane having silanol groups at both ends of the molecule, a crosslinking agent for silanol condensation, and a catalyst for silanol condensation to a heated and melted resin having a phenolic hydroxyl group. A resin composition having a phenolic hydroxyl group, characterized in that water is charged continuously or intermittently to carry out a crosslinking reaction of the organopolysiloxane in the resin having a phenolic hydroxyl group, and after the reaction is completed, water is removed. How things are manufactured. [Claim 2] The resin having a phenolic hydroxyl group is
A novolac type phenol resin obtained from a compound having a phenolic hydroxyl group and formaldehyde, a resol type phenol resin, and a polymer of the above compound having a phenolic hydroxyl group and paraxylylene dihalide or paraxylylene dialkyl ether. 2. The method according to claim 1, wherein the resin has a phenolic hydroxyl group selected from the group consisting of phenol aralkyl resin and naphthol aralkyl resin. [Claim 3] The emulsifier has the general formula (1) [Chemical formula 1] [Chemical formula 1]
] (In the formula, R' and R'' are the same or different C2 to C5 divalent hydrocarbon groups, and POA is ethylene oxide and/or
or a polyoxyalkylene group consisting of an adduct of propylene oxide, x is an integer from 200 to 990, y+z=1
0 to 800, and x+y+z<1000) or the compound represented by the general formula (2) [Chemical formula 2] [Chemical formula 2] (wherein R is a C4 to C12 alkyl group, and n is 1
An integer of ~20, EO indicates that ethylene oxide is added, PO indicates that propylene oxide is added, x and y are integers of 0 to 100, and 5≦x+y≦100
The manufacturing method according to claim 1, wherein the compound is a compound represented by: [Claim 4] Resin 10 having a phenolic hydroxyl group
0 parts by weight, the above general formula (1) or general formula (2)
4. The manufacturing method according to claim 3, wherein 0.01 to 25 parts by weight of an emulsifier represented by the following formula is added. [Claim 5] An organopolysiloxane having silanol groups at both ends of the molecule is represented by the general formula (3) [Chemical formula 3] [Chemical formula 3]
] (In the formula, R1 and R2 are the same or different monovalent hydrocarbon groups, alkyl groups including methyl, ethyl, propyl, butyl groups, phenyl groups, aryl groups including xylyl groups, γ-chloropropyl The method according to claim 1, wherein the compound is a halogenated monovalent hydrocarbon group containing a 3,3,3-trifluoropropyl group. [Claim 6] Resin 10 having a phenolic hydroxyl group
6. The manufacturing method according to claim 5, wherein 3 to 50 parts by weight of organopolysiloxane having silanol groups at both ends of the molecule represented by the general formula (3) is added to 0 parts by weight. 7. The crosslinking agent for silanol condensation contains three or more silicon atoms and a functional group selected from the group consisting of an alkoxy group, an acyloxy group, a ketoxime group, an alkenyloxy group, an aminooxy group, an amino group, and a hydrogen group. A polyfunctional silane directly connected to or having general formula (4) [Chemical formula 4]
The method according to claim 1, which is a methylhydrogenpolysiloxane represented by the formula: embedded image (where n is an integer from 3 to 10,000). [Claim 8] Resin 10 having a phenolic hydroxyl group
Claim 7: 0.05 to 5 parts by weight of the crosslinking agent for silanol condensation represented by the general formula (4) is added to 0 parts by weight.
Manufacturing method described. 9. The production method according to claim 1, wherein the silanol condensation catalyst is an organotin compound. 10. The production method according to claim 9, wherein 5 parts by weight or less of the organotin compound is added to 100 parts by weight of the organopolysiloxane having silanol groups at both ends of the molecule. [Claim 11] Resin 1 having a phenolic hydroxyl group
2. The manufacturing method according to claim 1, wherein 0.1 to 100 parts by weight of water is added to 0.00 parts by weight.