JPS63150345A - Glass fiber-reinforced phenolic resin composition - Google Patents

Abstract

PURPOSE:To provide the title compsn. which gives molded products having excellent strength, containing a phenolic resin as a matrix resin and specified glass fibers as a reinforcing material. CONSTITUTION:Glass fiber (a) is sized with a bundling agent (b) consisting of an aq. or self-dispersible novolak type and/or resol type phenolic resin as a tying agent, a coupling agent, a lubricant, an antistatic agent, a pH adjustor, etc., to obtain a reinforcing material (B). A novolak type and/or resol type phenolic resin (A), as a matrix resin, contg. optionally a curing agent (e.g., hexamethylenetetramine) is blended with the component B and optionally, a filler (e.g., woodmeal), a lubricant (e.g., stearic acid), a plasticizer (e.g., furfural), a colorant (e.g., carbon black), etc. (C). The mixture is kneaded while heating, cooled and crushed into a powder having a shape suitable for molding.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a new and useful glass fiber reinforced phenolic resin composition, and more particularly, to a glass fiber-reinforced phenolic resin composition that is sized with a phenolic resin as a binding agent. The present invention relates to a high-strength reinforced resin composition for molding, which uses fiber as a reinforcing component.

[Prior art and problems to be solved by the invention] Phenol resin is widely used as a molding material in the form of a kneaded mixture of fillers, lubricants, plasticizers, colorants, etc. It is one of the molding materials that is attracting attention because of its strength.

However, conventional glass fiber-reinforced phenolic resin compositions are not suitable for matrix resins, such as polyvinyl acetate, polyacrylate, polyurethane, polyester, or polyepoxy, as a binding agent constituting the glass fiber binding agent. Because Emulsion II is used, which is a resin that has poor compatibility with the phenolic resin, the adhesion between these glass fibers and the phenolic resin, which is the matrix resin, is insufficient, and as a result, sufficient strength cannot be achieved. The current situation is that it has not reached the point where it can demonstrate its full potential.

Under these circumstances, it has excellent convergence, and
There is a strong desire to develop a glass fiber-reinforced phenolic resin composition that can fully demonstrate the strength of the glass fiber itself by using a binding agent that is highly compatible with the phenolic resin for J-socks. .

[Means for solving problems]

Therefore, the inventors of the present invention conducted intensive research to obtain a glass fiber reinforced phenolic resin fabric that combines the various required properties as described above, and found that while a phenol resin is used as a matrix resin, a phenol resin is used as a sizing agent to bind the sizing material. A glass fiber-reinforced phenolic resin composition, which uses glass fibers that have been sieved by a chemical agent as a reinforcing material and contains these matrix phenolic resins and reinforcing materials as essential components, has been shown to provide high-strength molded products. This discovery led to the completion of the present invention.

In this specification, the terms binding agent and sizing agent are used, and the term "binding agent" is used for a substance that acts as a binder for sizing glass fibers. On the other hand, the term "bundling agent" is used as a general term for substances that serve various functions, such as coupling agents, lubricants, antistatic agents, or conditioning agents, in addition to such binding agents. I want to be understood as something.

In addition, in this specification, the binder constituting the sizing agent is referred to as "aqueous" or "self-dispersing".
The term phenolic resin is used, but the former term ``aqueous'' is used to include those that are diluted with water and exhibit water bath properties, and those that are emulsified with water and exhibit an emulsion state. On the other hand, it should be understood that the "self-dispersing type" is used for products that exhibit an emulsion state simply by diluting with water.

Examples of the above-mentioned matrix resins used in obtaining the glass fiber reinforced phenolic resin composition of the present invention include tumelac type phenolic resins and resol type phenolic resins. There are novolak/hexa-based systems consisting of tumerac-type phenolic resin and hexamethylenetetramine (hereinafter abbreviated as hexamine) as a curing agent, resol-based systems that use only resol-based phenolic resins, and both types of It is divided into Norac/Resol type, which uses resin in combination.

Next, the reinforcing material used in obtaining the reinforced resin composition of the present invention and referred to in the present invention is glass fiber sized with a sizing agent containing a specific sizing agent called phenolic resin. First, examples of the phenolic resin for the sizing agent used in this case include water-based or self-dispersing phenolic resins.

Here, regardless of whether the phenolic resin is of the Tumerac type or the resol type, ■ an emulsion type phenolic resin that is emulsified using a protective colloid and/or an emulsifier, and ■ water. Water-bathable phenolic resins that are diluted with water to form a water-bathable state, that is, in the form of a water-bath solution, or -■ Self-emulsifying or self-dispersing resins that are themselves diluted with water and emulsified or separated. There are three types of phenolic resins with

Among these, it is particularly effective to use a cationic or nonionic type aqueous or self-dispersing phenolic resin that has excellent compatibility with the coupling agent in the sizing agent.

To further explain the type of phenolic resin listed above, whether it is Noblak type or resol type, protective colloids and/or emulsifiers are added before, during or after the synthesis reaction. It is a water-based phenolic resin of emulsified carbon type.

Among these, particularly preferred is JP-A-55-7
As disclosed in Japanese Patent Application No. 174, 7 etsu/I/
This is a cationic sol resin emulsion obtained by condensation polymerization of aldehydes and aldehydes under an alkali catalyst.

The emulsilane thus obtained has good water dilution stability and also has excellent compatibility with coupling agents.

In addition, to further explain the above-mentioned type phenolic resin, whether it is a noblack type or a resol type, the reaction of both types of resins can be controlled in the state of a water bath, or the reaction of both types of resins can be controlled in a water bath state. It is obtained by adding a water-soluble organic solvent etc. to
They themselves are "water bathable and stable, and also stable even when diluted with water."

Furthermore, to add an explanation to the type of phenolic resin mentioned above, whether it is a noblack type or a resol type, a part of the structure of both types of resin, that is, a hydroxyl group or a methylol group, A self-emulsifying type that is obtained by reacting a water bathing compound or diluting both types of resin with a water-soluble organic solvent, and emulsifying or dispersing only after being diluted with water. It is.

Furthermore, the glass fibers used in obtaining the resin composition of the present invention are made by spinning molten glass into filaments, and then bundling several hundred of these filaments into a single strand. Furthermore, dozens of such strands are gathered together to form a roving, which is also referred to as a roving, but at this time, between the glass fibers,
Alternatively, in order to protect the filament by preventing yarn breakage and fuzzing caused by contact or friction between the glass fiber and mechanical parts such as guide eyes or rollers, a sizing agent containing a sizing agent as described above may be used. The products obtained by sizing are particularly referred to.

Here, to explain the above-mentioned chain components that make up the sizing agent, firstly, coupling agents are agents used for the purpose of improving the adhesion between resin and glass, and are mainly silane-based agents. , among which acrylic silane and vinyl silane.

Examples of the aminosilane/magazine include epoxysilane.

Next, the lubricant is used for the purpose of imparting lubricity to the yarn during sizing, and examples thereof include alkylimidacillin derivatives, polyoxyethylene or tetraethylenepentamine derivatives.

Antistatic agents are used to remove static electricity generated by friction, and include quaternary ammonium salts and inorganic salts.

Furthermore, the PH adjuster is used for the purpose of adjusting the coupling agent's t-adjustment, and examples thereof include aqueous ammonia and acetic acid.

The aAm fabric of the present invention uses the various components listed above, that is, the matrix resin, resin, and reinforcing material are the essential components. Using substances selected from various additive components such as additives, lubricants, plasticizers, and colorants, these are blended and premixed in a Banbury mixer, etc., and then heated in a heat roller A/or extruder, etc. Heat and knead thoroughly.
It is then taken out, cooled, and crushed into a shape suitable for molding.

The glass fiber-reinforced phenolic resin composition thus obtained can be easily molded by compression molding, transfer molding, extrusion molding, or the like.

Here, the above-mentioned fillers include wood flour, cotton flock, methylcellulose, soybean flour, paper, and hemp.

Vegetable fillers such as ligni/or cotton cloth, or asbestos, mica, diatomaceous earth, clay, rock wool, mica.

Inorganic fillers such as kaolin, gypsum or plastron powder are used.

In addition, the lubricants mentioned above are not limited to %, but representative ones include stearic acid,
Examples include higher fatty acids such as palmitic acid, their calcium salts, alkaline earth metal salts such as magnesium salts, montanic acid wax, and amides of the above-mentioned higher fatty acids.

Further, as the above-mentioned plasticizers, conventional ones such as furfural, alkylphenol, tricresyl phosphate, polyethylene glycol, dibutyl phthalate, or p-)luenesulfonamide are effective.

Furthermore, as the above-mentioned coloring agent, car? Black, spirit black, molybdenum red, phthalocyanine blue, phthalocyanine green, and handy yellow can be used.

〔Effect of the invention〕

The glass fiber-reinforced phenolic resin composition of the present invention provides a phenol resin molded product that can fully exhibit the strength of glass fiber as a reinforcing material, and can also provide extremely high strength performance.

〔Example〕

The present invention will be specifically explained below with reference to Reference Examples, Examples, and Comparative Examples, where all parts and 5 are based on weight unless otherwise specified.

Reference Example 1 [Example of Preparation of Binding Agent] In a 4-hour flask equipped with a stirrer, a thermometer, and a reflux condenser, 540 parts of phenol, 850 parts of 41% formalin,
54 of "Epinox P-130J C Dick Herkieles ■Cracked polyamide-epichlorohydrin resin"
25 parts of hydroxyethyl cellulose and 50 parts of barium hydroxide were charged, stirred and reacted at 80°C for 2.5 hours, and then 500 parts of water was added to the thus obtained resol type phenolic resin to disperse it. . After that, 60 parts of p-toluenesulfonic acid was added thereto to adjust the pH to 5, resulting in a homogeneous resol type phenol #4.
m Obtain fat emulsion silane.

This product has a solid content concentration (hereinafter abbreviated as NV) of 4.
At 0.1%, the Pruck Field viscosity (hereinafter abbreviated as viscosity) at 25° C. was 1,150 cps, and the pH was 5.0. Hereinafter, this will be abbreviated as RE-1.

Reference Example 2 (same as above) In a reaction vessel similar to Reference Example 1, 540 parts of phenol, 4
900 parts of 1% formalin and 5 parts of 48% sodium hydroxide aqueous solution were charged and reacted at 65°C for 2.5 hours, then at the same temperature for 4 hours until the viscosity of one donor at 25°C reached 1. Dehydrated under reduced pressure, then 35 days
After adjusting the pH to 7.0 with % hydrochloric acid, the mixture was rapidly cooled, and a mixed solvent of methanol/water = 600/400 (weight ratio) was added to obtain a water-bathable resol type phenol resin. This was a water bath liquid with an NV of 40%, a viscosity of 50 cps, and a - of 7.0. Below, this is R8-1
It is abbreviated as

Reference Example 3 (same as above) In a reaction vessel similar to Reference Example 1, 540 parts of phenol, p
- 156 parts of aminophenol, 4 parts of 41% formalin
41 parts and 156 parts of 35% hydrochloric acid were charged and heated to 100°C.
The reaction was then carried out at the same temperature for 4 hours until the viscosity of one donor at 25°C became I. Then, the pH was adjusted to 5.0 with 28% aqueous ammonia, and after cooling, ,000 parts of methanol was added to obtain a self-emulsifying noblack type phenolic resin.

This one has an NV of 40%, a viscosity of 100 cps,
It was a Nozerac type phenol resin solution with -5.0. Hereinafter, this will be abbreviated as MS-1.

Reference Example 4 (same as above) "Usage sound of Evinox P-1304 - The same operation as in Reference Example 1 was repeated except that the sound of Evinox P-1304 was cut off to obtain a nonionic resol type phenolic resin Emulzo M/. NY is 40.5%, viscosity is 1,200 ep
It was an emulsion tank with s and -5.0. Hereinafter, this will be abbreviated as RE-2.

Reference Examples 5 to 11 (Example of Preparation of Bundling Agents) Using the binding agents of Kukin 1 obtained in Reference Examples 1 to 4 and the binding agents for control as shown in Table 1, γ as a coupling agent was used. -Aminopropyltriethoxysilane and "Silazole 85AJ (Imperial Chemical Indus, UK) IJ-S Ltd. product" as a lubricant.
Using the following formulation and according to Table 1, first add 50 parts tying agent 6 parts coupling agent 0.3 parts lubricating agent
Add 0.15 parts of water to about 100.00 parts of water in advance in a mixing tank, add binding agent while stirring, then add lubricant, then add coupling agent, and then add acetic acid to make the mixture. -i 6
．． Adjusted to 0. Next, the remaining water was added to obtain various desired sizing agents.

Reference Examples 12 to 18 (Example of Preparation of Reinforcing Materials) E sized the lath using each of the sizing agents obtained in Reference Examples 5 to 11, and wound it into a cake cone.

The sizing agents used at that time are shown in Table 2.

Next, each of the glass fibers was dried in a conventional manner until the moisture content became 0.55 or less, and cut to obtain various kinds of sulfuric acid strides, that is, entire reinforcing materials.

Examples 1 to 5 and Comparative Example 1.2 Reinforcement material (chipped strand) 1
00 parts Matrix resin 100
Part hexamine O or 15 parts 20
2 or 217 parts The above ingredients are blended according to the locations shown in Table 3, kneaded for 4 minutes using hot rolls adjusted to 130°C/140°C, and then pulverized using a granierator. Every customer receives a lath fiber-reinforced phenolic resin composition.

Thereafter, each reinforced resin composition was molded using a transformer molding machine under curing conditions of 165° C. for 5 minutes.

However, only in the case of Example 5, instead of using a novolak/hexa system with Sogelac resin/hexamine = 100715 (weight ratio), "Prior 7 En KH3819
Except that 100 parts of J (solid resol type phenolic resin manufactured by Dainippon Ink & Chemicals ■) was used, and the crosstalk conditions using a hot roll were changed to 120° C. and 7130° C. for 5 minutes.

I did exactly the same as above.

Next, test pieces were cut out from each molded product and JI
S K-6911K Therefore, the tensile strength, bending strength, and impact strength were measured and are summarized in the same table.

Claims (1)

[Scope of Claims] 1. A glass fiber reinforced phenol comprising a phenol resin as a matrix resin, a phenol resin as a sizing agent, glass fibers sized by the sizing agent as a reinforcing material, and both of these components as essential components. Resin composition. 2. The resin composition according to claim 1, wherein the phenolic resin for a sizing agent is a novolac type phenolic resin. 3. The resin composition according to claim 1, wherein the phenolic resin for a sizing agent is a resol type phenolic resin. 4. The resin composition according to claim 1, wherein the phenolic resin for a sizing agent is a mixture of a resol-type phenolic resin and a resol-type phenolic resin. 5. The resin composition according to claim 1, wherein the phenolic resin for the matrix resin is a novolac type phenolic resin. 6. The resin composition according to claim 1, wherein the phenolic resin for the matrix resin is a resol type phenolic resin. 7. The resin composition according to claim 1, wherein the phenolic resin for the matrix resin is a mixture of a novolac type phenolic resin and a resol type phenolic resin.