JPH0688031A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:To obtain a thermosetting resin composition which can give a molding excellent in staining resistance without detriment to the moldability, electrical properties, mechanical properties, heat resistance, etc., by mixing a thermosetting resin with a specified substance and an oxide of a (non)metal in a specified mixing ratio. CONSTITUTION:The composition comprises 100 pts.wt. thermosetting resin (e.g. novolac phenolic resin), 1-100 pts.wt. substance having a critical surface tension of 31dyn/cm or below at 23 deg.C, desirably a fluororesin or a silicone resin (e.g. polytetrafluoroethylene), and 20-150 pts.wt. oxide of a (non)metal selected from among Zn, Al, Si, Ti, Sn, Fe, Ni and Mn (e.g. rutile titanium oxide).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a thermosetting resin composition suitable for producing a thermosetting resin molded product having excellent stain resistance.

[0002]

2. Description of the Related Art Thermosetting resins are excellent in electrical properties, mechanical properties, heat resistance, flame resistance, etc., so that their molded products are used in the paper industry, textile industry, machine industry, food industry, photographic industry, etc. It is used as a device or its parts in a wide range of fields.

However, various molded products of thermosetting resins include metal oxides such as iron oxide, silver oxide and copper oxide, non-metal oxides such as zinc oxide and tin oxide, or colloidal substances thereof.
Contaminated with inorganic salts such as sulfate, potassium salt, calcium salt, sodium salt, glycine, alanine, cysteine, phenylalanine, cystine, methionine, tyrosine, collagen, proline, glutamic acid, tryptophan, leucine, oils, etc., The function as a device or a part may be deteriorated.

Various molded products of contaminated thermosetting resin are
It is cleaned by a chemical treatment such as immersion in a solution or solvent of strong acid, strong alkali, oxidizing agent, reducing agent or the like.
However, the surface of various molded products of thermosetting resin may be affected by the chemical treatment. Further, washing with a physical method such as high-pressure water washing or graft treatment is effective for removing contaminants, but may be damaged.

Both methods require a great deal of labor and time to remove and clean the contaminants, which is a factor of impairing the productivity.

Therefore, as a method for preventing contamination of various molded products of thermosetting resin, for example, Japanese Patent Application Laid-Open No. 2-1274.
JP-A-60 discloses a phenolic resin composition obtained by adding an inorganic filler and / or an organic filler to 100 parts by weight of a phenolic resin, and further adding 1 to 10 parts by weight of polytetrafluoroethylene. There is.
However, the molded product obtained from the composition does not always have a sufficient antifouling effect.

In the plastic material course 15, phenol resin (Nikkan Kogyo Shimbun Co., Ltd., 4th edition, page 152), 0 to 17 parts by weight of lime, magnesium oxide or the like is used as a curing accelerator with respect to 100 parts by weight of the phenol resin. It is described to be used. However, the molding material obtained by this method is also not a molding material having a sufficient contamination preventing function.

Further, Japanese Patent Laid-Open No. 4-149550 discloses a method of processing a silver halide photosensitive material using a roller made of a hydrophilic material having a contact angle with water of 40 degrees or less.

However, since the roller used in the method is hydrolyzable, a part of the constituent components of the roller is gradually eluted during use, the roundness of the roller is lowered and the outer diameter of the roller is changed. However, this method is not preferable because it has a drawback that the photosensitive material cannot be transported smoothly.

From such a background, various molded products of thermosetting resins having excellent stain resistance are desired.

[0011]

SUMMARY OF THE INVENTION The object of the present invention is to solve the above problems and to improve the stain resistance without deteriorating the characteristics such as moldability, electrical characteristics, mechanical characteristics, heat resistance and flame resistance. It is to provide a thermosetting resin composition which gives an excellent molded product.

[0012]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies in order to achieve the above object, and as a result, have found that a substance having a specific critical surface tension in a thermosetting resin and a specific metal or non-metal. A resin composition obtained by adding an oxide,
The present invention has been found out that a molded product excellent in stain resistance can be provided without impairing the original properties of the thermosetting resin.

That is, according to the present invention, the thermosetting resin 1
00 parts by weight, the critical surface tension at 23 ° C. is 31 dyn
1 to 100 parts by weight of a substance of e / cm or less, and zinc,
Provided is a thermosetting resin composition containing 20 to 150 parts by weight of a metal or non-metal oxide selected from the group consisting of aluminum, silicon, titanium, tin, iron, nickel and manganese.

If desired, the thermosetting resin composition of the present invention may further contain other additives such as a curing agent, a fiber reinforcing material, a filler, a lubricant and a coloring agent.

The method for producing the thermosetting resin composition of the present invention is not particularly limited, and a commonly used method for producing the thermosetting resin composition can be applied.

For example, a metal selected from the group consisting of a substance having a critical surface tension of 31 dyne / cm or less at 23 ° C. with respect to a thermosetting resin, zinc, aluminum, silicon, titanium, tin, iron, nickel and manganese. Or non-metal oxides, and optionally hardeners, fiber reinforcements,
After adding other additives such as fillers, lubricants, colorants, etc. and mixing them at room temperature or a temperature in the vicinity thereof using a mixer such as a ribbon blender, a Henschel mixer, a kneader, an ordinary mixing roll, twin screw A method of kneading using an extrusion kneader or the like, further heat treating if necessary, and then crushing using a crusher such as a power mill, or for the thermosetting resin, the above specific oxide, if necessary Hardener,
Add other additives such as fiber reinforcement, fillers, lubricants, colorants, etc., and use a mixer such as a ribbon blender, a Henschel mixer, or a kneader at room temperature or in the vicinity thereof, and then perform normal mixing. After kneading using a roll, twin-screw extrusion kneader, etc., further heat treating if necessary, and then pulverizing with a pulverizer such as a power mill, then at 23 ° C.
A method of adding and mixing a substance having a critical surface tension of 31 dyne / cm or less is exemplified.

The thermosetting resin composition of the present invention will be described in detail below. Examples of the thermosetting resin used in the present invention include phenol resin, melamine resin, aniline resin, epoxy resin, unsaturated polyester resin, melamine-phenol resin and furan resin.

In the present invention, the critical surface tension at 23 ° C. is defined in Kagaku Binran revised 2nd edition, basic edition II, page 618 (Maruzen Co., Ltd., published in 1975). That is,
Assuming that the contact angle θ indicated by the homologous series of liquid hydrocarbons and other organic liquid compounds on the solid surface and the surface tension of the liquid is γ,
The relationship between cos θ and γ is almost a straight line regardless of the type of homologue. At this time, the value of γ corresponding to θ = 0, that is, cos θ = 1 is defined as the critical surface tension of the solid.

In the present invention, all solids having a critical surface tension at 23 ° C. of 31 dyne / cm or less can be used. For example, polyfluoromethyl acrylate, polyfluoromethyl methacrylate, polyhexafluoropropylene, polytetrafluoroethylene, polyvinylidene fluoride, polychlorotrifluoroethylene,
Fluorine resins such as tetrafluoroethylene / propylene hexafluoride copolymers and polytrifluoroethylene, and the following general formula (1)
[Chemical 1]

[0020]

[Chemical 1] (In the formula, R ₁ and R ₂ are a methyl group, an ethyl group, a butyl group,
A phenyl group and a vinyl group are shown, and they may be the same or different. And a silicone-based resin having a repeating structural unit represented by the formula (1).

These fluororesins or silicone resins are used in order to improve the dispersibility with the thermosetting resin.
Those having a small particle size having an average particle size of about 50 μm are suitable. The critical surface tension at 23 ° C is 31 dyne
1 to 100 parts by weight of the substance having a density of not more than / cm is used per 100 parts by weight of the thermosetting resin. If it is less than 1 part by weight, the effect of stain resistance is small, and if it exceeds 100 parts by weight, moldability tends to deteriorate, so the above range is preferred.

Examples of the metal or non-metal oxide used in the present invention include zinc oxide, aluminum oxide, silicon oxide, titanium oxide, tin oxide, iron oxide, nickel oxide and manganese oxide. These oxides may be used alone or as a mixture thereof.

Although the above metal or non-metal oxide may be replaced with octadecylamine, hexadecane, perfluorokerosene, perfluorodecanoic acid, perfluorobutyric acid, 2-pentyltetradecanoic acid, etc., the antifouling effect is recognized. Since the effective period of the effect is limited, the above-mentioned metal or non-metal oxides are preferable in achieving the object of the present invention.

The metal oxide or non-metal oxide is used in an amount of 20 to 150 parts by weight based on 100 parts by weight of the thermosetting resin. If it is less than 20 parts by weight, the effect of preventing contamination is small, and if it exceeds 150 parts by weight, the moldability of the resin composition tends to deteriorate.

The thermosetting resin composition of the present invention is characterized in that the critical surface tension at 23 ° C. is 31 dyne / cm.
The specific amounts of the following substances and the above metal or non-metal oxides are used in combination. When used in combination, the composition gives a molded product having excellent stain resistance.

In the present invention, the fibrous reinforcing material optionally used is glass flakes in the form of scales having a size of 10 to 2000 μm, chopped strand glass having a size of 1 to 6 mm, headman fibers, ceramic fibers, wood powder, Examples include linter pulp, polyimide fiber, vinylon fiber, aromatic polyamide fiber, aromatic polyester fiber, carbon fiber, rock wool, potassium titanate fiber and the like.

The fiber reinforcing material is used in the range of 25 to 300 parts by weight with respect to 100 parts by weight of the thermosetting resin. 25
If it is less than 100 parts by weight, the strength of the obtained molded product is low, and if it exceeds 300 parts by weight, the moldability of the molded product is deteriorated. In addition, examples of the filler used as needed include kaolin, talc, diatomaceous earth, perlite, bentonite, magnesium carbonate, magnesia, basic magnesium silicate, magnesium carbonate, various silicates, and celite.

The above filler is used in the range of 10 to 150 parts by weight with respect to 100 parts by weight of the thermosetting resin. If it is less than 10 parts by weight, the strength of the molded product is low, and if it exceeds 150 parts by weight, the moldability becomes poor.

Further, hexamethylenetetramine (hereinafter abbreviated as hexamine) which is usually used as a curing agent for thermosetting resins is preferably used as a curing agent used as necessary. The amount of hexamine used is 8 to 18 parts by weight based on 100 parts by weight of the novolac resin. If it is less than 8 parts by weight, it will be difficult to obtain a satisfactory molded product, and if it exceeds 18 parts by weight, the surface roughness of the molded product will be poor.

It is not necessary to add the curing agent when the resol type phenol resin is used alone as the thermosetting resin, or when the novolac type phenol resin and the resol type phenol resin are used in combination.

The lubricant is not particularly limited, but higher fatty acids such as stearic acid and palmitic acid, alkaline earth metal salts (calcium salts, magnesium salts, etc.) of the higher fatty acids, montanic acid wax, amides of the higher fatty acids. A class can be used. The lubricant may be added by mixing with a resin or the like, or may be added after adjusting the composition in some cases.

As the colorant, carbon black, spirit black, molybdenum red, phthalocyan blue,
Phthalocyan green, Hansa yellow, etc. are appropriately selected and used.

The thermosetting resin composition of the present invention thus obtained can be applied to any molding method such as compression molding, injection molding, transfer molding or extrusion molding. For example, in the case of molding using an injection molding machine or an extrusion molding machine, for example, by increasing the friction on the barrel surface by forming a groove on the barrel surface, etc., the penetration of the resin composition into the screw becomes good. It enables stable molding.

The present invention will be described below with reference to Examples and Test Examples.
A more specific description will be given.

[0035]

【Example】

Example 1 Novolak type phenolic resin (manufactured by Mitsui Toatsu Chemicals, Inc.,
Product name: # 2000) 100 parts by weight, hexamine (manufactured by Mitsui Toatsu Chemicals, Inc., product name: S-4) 12 parts by weight, glass fiber (manufactured by Nippon Electric Glass Co., Ltd., product name: ECS-03
B) 100 parts by weight, rutile-type titanium oxide (for industrial use) 80
40 parts by weight of polytetrafluoroethylene (Kitamura Co., Ltd., trade name: KTL-610), 3 parts by weight of zinc stearate, and 3 parts by weight of carbon black are mixed for 20 minutes at room temperature using a ribbon blender. did. The obtained mixture was roll-kneaded for about 3 minutes using a mixing roll having a front roll temperature of 95 ° C and a rear roll of 50 ° C. The resulting mixture was crushed into Daltons using a power mill,
It heat-processed at 8 degreeC-83 degreeC for 8 hours, and obtained the thermosetting resin composition.

Example 2 100 parts by weight of resol type phenol resin (manufactured by Gunei Chemical Industry Co., Ltd., trade name: N-411), calcium hydroxide (manufactured by Iriko Sangyo Co., Ltd., trade name: TG-200) 1.5 parts by weight, glass fiber (Nippon Electric Glass Co., Ltd., trade name: E
CS-03B) 70 parts by weight, silicon dioxide (manufactured by Seto Ceramic Materials Co., Ltd., trade name: Seyogen FS) 110 parts by weight, zinc stearate 3 parts by weight, carbon black 3 parts by weight at room temperature using a ribbon blender. Mix for 20 minutes. The obtained mixture was roll-kneaded for about 3 minutes using a mixing roll having a front roll temperature of 95 ° C and a rear roll of 50 ° C. The mixture was pulverized into Daltons using a power mill, and 30 parts by weight of a tetrafluoroethylene-hexafluoropropylene copolymer (manufactured by Kitamura Co., Ltd., trade name: KTL-500F) was used at room temperature using a ribbon blender. And mixed for 20 minutes to obtain a thermosetting resin composition.

Example 3 Diallyl phthalate resin (manufactured by Daiso Co., Ltd., trade name:
DAP-A) 100 parts by weight, dicumyl peroxide 1
Parts by weight, glass fiber (manufactured by Nippon Electric Glass Co., Ltd., trade name:
ECS-03B) 90 parts by weight, ferric oxide 40 parts by weight,
100 parts by weight of light calcium carbonate (manufactured by Takehara Chemical Industry Co., Ltd.), polytetrafluoroethylene (manufactured by Kitamura Co., Ltd.,
Trade name: KTL-610) 40 parts by weight, zinc stearate 3 parts by weight, and carbon black 3 parts by weight were mixed for 20 minutes at room temperature using a ribbon blender. The obtained mixture was roll-kneaded for about 3 minutes using a mixing roll having a front roll temperature of 85 ° C and a rear roll of 50 ° C. The mixture was ground using a power mill (manufactured by Dalton Co., Ltd.) to obtain a thermosetting resin composition.

Example 4 Novolak type phenolic resin (manufactured by Mitsui Toatsu Chemicals, Inc.,
Trade name: # 2000) 100 parts by weight, hexamine (manufactured by Mitsui Toatsu Chemicals, Inc., trade name: S-4) 12 parts by weight, silicone resin powder (manufactured by Toray Dow Corning Co., Ltd., trade name: F-100) ) 50 parts by weight, rutile type titanium oxide (for industrial use) 40 parts by weight, glass fiber (Nippon Electric Glass Co., Ltd.)
Product name: ECS-03B) 100 parts by weight, kaolin (manufactured by Tsuchiya Kaolin Co., Ltd.) 40 parts by weight, sodium stearate 3 parts by weight, carbon black 3 parts by weight are mixed for 20 minutes at room temperature using a ribbon blender. did. The obtained mixture was roll-kneaded with a mixing roll having a front roll temperature of 95 ° C. and a rear roll of 50 ° C. for about 3 minutes. The mixture was ground using a power mill (manufactured by Dalton Co., Ltd.) to obtain a thermosetting resin composition.

Comparative Examples 1 to 3 and 5 to 6 The same treatments as in Example 1 were carried out at the mixing ratios shown in Table 2 to obtain thermosetting resin compositions.

Comparative Example 4 A thermosetting resin composition was obtained by treating in the same manner as in Example 3 with the mixing ratios shown in [Table 2].

The composition and evaluation test results of the thermosetting resin compositions obtained in Examples 1 to 4 are shown in Table 1. The composition of the thermosetting resin compositions obtained in Comparative Examples 1 to 6 and the results of evaluation test results are shown in [Table 2].

Evaluation tests of various characteristics of the thermosetting resin compositions obtained in Examples and Comparative Examples were carried out by the following methods.

Preparation of Test Pieces Toshiba Machine Co., Ltd., Model: IR45P type injection molding machine, cylinder temperature 1st zone 60 ° C, 2nd zone 9
JIS-K-691 under conditions of 0 ° C., mold temperature fixed side 160 ° C., moving side 165 ° C., screw rotation speed 50 rpm.
According to the method specified in 1, test pieces for evaluation of bending strength, insulation resistance, heat resistance and flame resistance were prepared. Further, similarly, a test piece for a stain resistance test was prepared according to the method for preparing a test piece for measuring water absorption rate specified in JIS-K-6911.

Contamination test Commercially available photographic developer (Konica Corporation, trade name: SRX-
After dissolving silver bromide in 501) to a saturated solubility and immersing the test piece in the solution for 3 months at 30 ° C., the following two kinds of staining properties were tested. Add 20 ml of 6N nitric acid solution to a beaker with 30 ml of silver adhesion,
The treated test piece (total surface area 8 cm ² ) was immersed in the solution and left at room temperature for 48 hours to elute the adhered silver. A light source current of 1 was used for the eluate using an atomic absorption spectrometer (manufactured by Nippon Jar Ash Co., Ltd., model: AA-1 type).
Analysis was performed under the conditions of 0 mA, a slot capillary, and an air / hydrogen flame, and the amount of attached silver was quantified. Potassium adhesion amount After gold vapor deposition was performed on one surface of the treated test piece, the surface was irradiated with an electron beam under the condition of an accelerating voltage of 20 KV and 225 mA, and accumulated 30 times (manufactured by Shimadzu Corporation, Electron beam microanalyzer, type: EPMA) The strength of the attached potassium was measured. Bending strength, insulation resistance, heat resistance and flame resistance test Measured according to the method specified in JIS K-6911.

[0045]

[Table 1]

[0046]

[Table 2]

[0047]

By using the thermosetting resin composition of the present invention, a molded product having excellent stain resistance can be obtained, and further, moldability, electrical properties, mechanical properties, heat resistance and flame resistance are obtained. And so on.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akio Kashino 1 Hino City, Hino City, Tokyo Konica Stock Company Hino Works (72) Inventor Akira Tokyo 1, Hino City Sakura City, Kino Stock Company Hino Works Co., Ltd.

Claims (2)

[Claims] 1. A material having a thermosetting resin of 100 parts by weight and a critical surface tension at 23 ° C. of 31 dyne / cm or less.
100 parts by weight and zinc, aluminum, silicon,
A thermosetting resin composition containing 20 to 150 parts by weight of a metal or non-metal oxide selected from the group consisting of titanium, tin, iron, nickel and manganese. 2. The critical surface tension at 23 ° C. is 31 dy.
The thermosetting resin composition according to claim 1, wherein the substance having a ne / cm or less is a fluororesin or a silicone resin.