JPS601243A - Composition for resin treatment - Google Patents

Abstract

PURPOSE:To provide the titled compsn. having excellent compatibility, blending stability, film properties and adhesion, containing a synthetic rubber latex having a specified particle size and a resol type phenolic resin emulsion. CONSTITUTION:One mol of a phenol is reacted with 1-3.5mol of formaldehyde in the presence of a basic catalyst and a monionic emulsifier having an HLB value of 8-18 and/or a water-soluble high-molecular material to an appropriate degree of condensation, and the reaction mixture is diluted with water. The pH thereof is adjusted with an inorg. or org. acid to 4-6, thus obtaining a resol type phenolic resin emulsion (A) having an average particle size of 0.3-3mum and contg.resin component at a concn. of 1-60wt%. A synthetic rubber latex (B) having an average particle size of 0.2mum or above composed of 10-99.5wt% butadiene, 0.5-10wt% ethylenically unsaturated carboxylic acid and 0-89.5wt% other vinyl monomer is blended with component A in a weight ratio of 1/99- 99/1.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel and useful composition for resin processing,
More specifically, it contains synthetic rubber latex with a specific particle size range and emulsion R of resol type phenolic resin as essential components, and has excellent compatibility, blend stability, film properties, and adhesive properties. , respectively, relates to a composition particularly useful for resin processing that takes advantage of the features of both components.

Here, the respective features of the synthetic rubber latex and the resol type phenolic resin emulsion are, as is well known, the former latex has flexibility, and the latter emulsion has heat resistance and resistance. It has excellent solvent resistance, water resistance, weather resistance, etc. Therefore, the purpose of the present invention is to first develop a useful composition that takes full advantage of these advantages and also provides new performance. It is not intended to be provided.

In recent years, the scope of use of various resins has expanded to a wide range, and the advancement of technology has become even more remarkable, and it is no longer possible to meet the performance requirements of each case by simply pursuing the characteristics of a single resin. In order to meet these required characteristics, we have taken measures to modify the properties through chemical reactions, reactions, and blends with different types of substances.In particular, resins that are compatible with other resins in good conditions are extremely valuable. It can be said that it is a valuable existence.

By the way, it is also known that phenolic resins are used for molding, casting, stacking adhesives, coatings, etc.
On the other hand, it is already well known that synthetic rubber latex is used for paper fibers, adhesives, coatings, cement mixtures, dip molding, etc.
The performance requirements for these resins are also diverse, and these requirements cannot be met with a single resin alone (
There is a growing need to respond to these demands by providing superior properties through various formulations.

Under these circumstances, in order to fully respond to the characteristics required each time and satisfy the requirements, no matter what equipment is used, it is necessary to have good formulation stability and uniform miscibility. It can be said that this is the first prerequisite and an extremely important factor. Therefore, the inventors of the present invention focused on blending these phenolic resins and synthetic rubber latex, and as a result of their intensive research, they blended synthetic rubber latex with a specific particle size with Emulsilon, a resol type phenolic resin. The composition should not only fully satisfy the above-mentioned prerequisites, but also be able to take advantage of the characteristics of each component, and be most effective in terms of performance. The processed base material has excellent coating properties and adhesive strength,
Moreover, they discovered that it has excellent heat resistance and water resistance, and have completed the present invention.

That is, the present invention provides a resin processing composition comprising as essential components a synthetic rubber latex each having an average particle diameter of 0.2 μm or more and a resol type phenolic resin emulsion having an average particle diameter of 0.3 to 3 μm. .

Here, the resol type phenolic resin emulsilon (hereinafter abbreviated as resol emulsilon) mentioned above refers to a nonionic emulsifier such as polyoxyalkyl phenol ether and/or a nonionic emulsifier such as polyvinyl alcohol or hydroxyethyl cellulose. The average particle diameter of the dispersed particles stabilized by the water-soluble polymer substance is 0.3 to 3 μm, preferably 0.5 to 1
．． It refers to 5 μm.

If this average particle size is less than 0.3 μm, it will not only be difficult to obtain a resin emulsilon, but also the obtained emulsilon will have a high viscosity, which will impede workability. If it exceeds 3 μm, not only will the stability of the resin emulsilon be impaired, but it will also have poor compatibility when mixed with the synthetic rubber latex, and it will be difficult to obtain a base material by resin processing using a composition in such a state. Products (processed products) produced by this process are undesirable because they have inferior physical or chemical properties.

In addition, it is preferable that the resol/emulsilon contains a phenol resin in which the phenol nucleus mainly consists of two or more nuclei, especially three to four nuclei, and the molecular weight indicates a preferable phenol resin. Then, 300
It has a number average molecular weight of 2,500 to 2,500, more preferably 400 to 1,000.

Any known and commonly used resol/emulsilon can be used as long as the average particle diameter of the dispersed particles is within the range of 0.3 to 3 μm. can be easily manufactured.

That is, in the presence of a nonionic emulsifier and/or a water-soluble polymer substance with an HL B value of 8 to 18, 1 to 3.5 moles of formaldehyde, preferably 1. 7 to 2.5 moles are reacted using an ordinary basic catalyst, diluted with water when a certain degree of condensation is reached, and p-condensed with an inorganic or organic acid.
By adjusting l+ to 4 to 6, the desired stable resol emulsion can be obtained.

Here, typical nonionic emulsifiers mentioned above include polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene alkyl ester, and polyoxyethylene alkyl ether.
Polyoxypropylene block copolymer, so-called
Pluronic" type surfactants [manufactured by Asahi Denka Kogyo Co., Ltd.], etc.; on the other hand, typical water-soluble polymer substances mentioned above include polyvinyl alcohol, droxyethyl cellulose, or partially hydrolyzed polyvinyl acetate, etc. There is.

The amount of these nonionic emulsifiers and/or water-soluble polymer substances used is usually 1 to 10% by weight, preferably 2 to 10% by weight based on the above-mentioned phenolic resin content.
A range of 5% by weight is suitable.

Typical phenols mentioned above include phenol, cresol, xylenol, and other alkylphenols including resorcinol, while typical formaldehydes mentioned above include formalin and paraformaldehyde. The above-mentioned basic catalysts include alkali metal or alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide, barium hydroxide or calcium hydroxide, ammonia or triethylamine or triethanolamine. Although there are amines, these catalysts are usually used in a ratio of 0 to 1 mole of phenols.
．． It is used in a proportion of 0.01 to 0.1 mole.

Furthermore, representative acids for pH adjustment include inorganic acids such as hydrochloric acid, sulfuric acid or phosphoric acid, and organic acids such as formic acid, oxalic acid, lactic acid or para-toluenesulfonic acid.

The resol emulsilone, which is an essential component of the composition of the present invention, is obtained, and the particle size is adjusted so that the HLB value used during the preparation of the emulsilone is 8 to 1.
8. This can be achieved by using a nonionic emulsifier in a certain range, preferably from 10 to 16, and by maintaining a constant dilution ratio with water. In this case, the use of the nonionic emulsifier is limited to only one type. The average HLB value of two or more types is 8.
It is also possible to combine them as appropriate so that the range falls within the range of 1B to 1B.

In this way, a desired emulsion with a resin concentration of 1 to 60% by weight can be obtained, and the preferred resin concentration of the emulsion is in the range of 3'' to 50% by weight.

Next, synthetic rubber latex having an average particle size of 0.2 μm or more is already well known and can be prepared by the method described below, but in the present invention, synthetic rubber latex obtained by any of the manufacturing methods will be used. It can also be used.

In the first step, 5 to 25% by weight of the total monomer mixture is added to 30 to 10% of the total monomer mixture.
A method of obtaining a latex with a large average particle size by emulsion polymerizing until 0% of the monomer is polymerized, and then emulsion polymerizing the remaining (95 to 75% of the total monomer mixture) weight monomer in the second step (Japanese Patent Publication No. 1973) (2) While using a water-soluble peroxide as a polymerization initiator, ethylenediaminetetraacetic acid or its salt is further added from the beginning of the polymerization or during the polymerization.
A method of obtaining latex with a large average particle size by employing special polymerization conditions of emulsion polymerization at ~80°C (Japanese Patent Publication No. 48-6186, etc.), (3) Using fatty acid soap or rosin acid soap as an emulsifier. , the monomer/water ratio is 0.8 to 1.5,
and in emulsion polymerization at a temperature of 30°C or higher, it has a molecular weight of 1103 or higher and has a solubility at room temperature of at least 2 x 10''-g per 100 g of water.
100% nonionic water-soluble polymer colloidal substance
Mg5Ca and Zn are added at a ratio of 0.00001 to 0.1 g per g, and Mg5Ca and Zn are added as necessary.

I x 10 per 100 g of monomer using water-soluble salts of metals Sr, Cd and/or Ba as metal ions
-! A special method disclosed in Japanese Patent Publication No. 49-7078, etc., in which a latex with a large average particle size is obtained by adding and gelating at a ratio of ~lXl0-3g atoms, or (41CaXZn, Sr, Cd and/or Ba
A water-soluble salt of a metal is added as a metal ion in a proportion of I x 10' to 1xlO'' g atoms per 100 g of monomer, and then a water-soluble alginate is added as a metal ion in a proportion of I x 10' to 1 x lO'' g atoms per 100 g of monomer. A special method as shown in Japanese Patent Publication No. 49-7077, in which emulsion polymerization is carried out in the same manner as in the previous section (3), except that the components are added and diluted in such a proportion, can be mentioned.

And, in making 11 of the synthetic rubber latex,
The monomer composition constituting the synthetic rubber is usually 1
0-99.5% by weight, preferably 20-60% by weight of butadiene, and 0.5-10% by weight or 1-54% by weight.
16 ethylenically unsaturated carboxylic acids and 0 to 89.5% by weight of other vinyl monomers.

Here, typical examples of the diethylenically unsaturated carboxylic acids include monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, or citrate monocarboxylic acid; dicarboxylic acids such as itaconic acid, fumaric acid, or maleic acid. Examples include acids, anhydrides or monoalkyl esters of these dicarboxylic acids.

Typical examples of the other vinyl monomers mentioned above include methyl, ethyl, and ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, and
Alkyl esters such as n-propyl, i-propyl, n-methyl, t-methyl or 2-ethylhexyl, or alkyl esters having a functional group such as 2-hydroxyethyl or glycidyl; styrene, α-
Unsubstituted, α-substituted or nuclear substituted styrenes such as methylstyrene, p-methylstyrene, p-methoxystyrene, 0-chlorostyrene or p-chlorostyrene; or vinyl chloride, vinyl bromide, vinylidene chloride, acrylamide , N-methylolated acrylamide or vinylpyridine.

The composition for resin processing of the present invention is prepared by blending the synthetic rubber latex, each of which is an essential component, obtained as described above, and resol/emulsilon at a mixing ratio of 1/99 to 99/1. However, the composition of the present invention thus obtained may further contain various known and commonly used additives, if necessary.

In order to apply the composition of the present invention to a substrate, the substrate of this type may first be soaked in a liquid bath containing the composition of the present invention, such as by spraying, roller coating or knife coating. It may be applied by a coating method or by an internal addition method.

Here, typical base materials to which the resin processing composition of the present invention can be applied include single IQ or JLI
Each of these materials includes natural or synthetic organic fibers or inorganic fibers such as glass fibers or ceramic fibers, woven fabrics, non-woven fabrics, paper, asbestos, metal plates such as iron plates, or foams of natural or synthetic polymers.

Next, the present invention will be specifically explained using reference examples, examples, and comparative examples, and unless otherwise specified, all parts and percentages are based on mold cost.

Example 11 Preparation of resol emulsion) In a stainless steel reaction vessel equipped with a stirrer, a condenser and a temperature needle were attached, and 270 parts of phenol, 414 parts of 41% formalin and [Neugen E-130TJ (No. 6 parts of polyoxyethylene nonylphenyl ether, I (LB = 13) manufactured by Yaku911 were charged, and 18 parts of hydroxyethyl cellulose was gradually added and dissolved while stirring, followed by 27 parts of barium hydroxide.
of the mixture was added and reacted at 80'C for 3 hours.

Next, 448 parts of water was added to the resol type phenol resin obtained in this way to cause coagulation and dispersion, and then 35 parts of para-toluenesulfonic acid was added to adjust the pFI to 5.0.
A homogeneous emulsion was obtained.

The resol emulsion obtained here has a solid content concentration of 39.4%, a viscosity of 720 cps, and a po of 5.0.
And the average particle diameter of the dispersed particles was 1.6 μm.

Hereinafter, this emulsilon will be abbreviated as RE-1.

Reference Example 2 (same as above) A condenser and temperature needle were attached to a container similar to Reference Example 1, and 500 parts of phenol and 7 parts of 41% formalin were added.
74 parts, "Neugen E-120J (polyethylene glycol nonylphenyl ether i manufactured by the same company) IL
B = 12) and 4 parts of Neugen ES90J (manufactured by the same company, polyethylene glycol oleic acid ester i HL B = 9) were added, and while stirring, 25 parts of partially saponified polyvinyl alcohol and 8 parts of hydroxyl were added. After adding and dissolving ethyl cellulose,
Add 25 parts of 48% sodium hydroxide aqueous solution and heat to 75°C.
Then, 530 parts of water was added to the resol-type phenolic resin obtained in this way for coagulation and dispersion. After mixing, a homogeneous emulsion was obtained.

The solid content concentration of this resol emulsilon is 39.6%
The viscosity was 1600 cps, the pH was 4.6, and the average particle diameter of the dispersed particles was 0.9 μm. Hereinafter, this emulsion will be abbreviated as RE-2.

$1113 (phenol 4if fat emulsion 11
i ffl ) 500 parts of phenol, 774 parts of 41% formalin and 25 parts of 48% sodium hydroxide were added and reacted at 80°C for 2.5 hours, then cooled to 50°C, and at the same temperature [-Neugen ET80J (Polyethylene glycol oleyl ether manufactured by the same company, HL B
= 8.0) and 8 parts of hydroxyethyl cellulose were added and stirred uniformly, and then 530 parts of water was added to the resol type phenolic resin obtained as pl + 6.0 with 30 parts of hydrochloric acid to form a uniform emulsion. I got the liquid.

The resol phenol obtained here has a solid content concentration of 4
0.2%, the viscosity is 600 cps, and the pl( is 6.0
And the average particle diameter of the dispersed particles was 5.0 μm.

Hereinafter, this emulsilon will be abbreviated as RE-1'.

Reference Example 4 (11!i example of synthetic rubber latex) 35 parts of butadiene, 63 parts of styrene and 2 parts of methacrylic acid, 2 parts of polyoxyethylene alkyl ether sodium sulfonate as an emulsifier, and ethylenediaminetetraacetic acid. 0.1 part of potassium persulfate, 0.2 part of potassium persulfate and t
- Emulsified with 0.1 part of dodecyl mercaptan in 130 parts of ion-exchanged water and polymerized at 60°C for 15 hours with stirring to achieve a polymerization rate of 98% and a solid concentration of 4.
A seed latex of 3% was obtained.

Next, 35 parts of butadiene, 63 parts of styrene, and 2 parts of methacrylic acid were mixed with O, S of sodium polyoxyethylene alkyl ether sulfonate as an emulsifier.
S, 0.2 parts of ethylenediaminetetraacetic acid, 0.2 parts of potassium persulfate, 0.2 parts of t-dodecyl mercaptan, and 5 parts of seed latex were emulsified in 105 parts of deionized water and stirred. When polymerization was carried out at 60°C for 23 hours, a latex was obtained with a polymerization rate of 93%, but after removing unreacted monomers and concentrating it by vacuum distillation, the solid content concentration was 55% and the average particle size was reduced. is 0
．． A target latex of 25 μm was obtained.

Hereinafter, this latex will be abbreviated as L-1.

Reference Example 5 (same as above) 42 parts of butadiene, 56 parts of styrene, and 2 parts of acrylic acid were mixed with 0% of sodium laurate as an emulsifier.
．． 5 parts, 0.2 parts of ethylenediaminetetraacetic acid, 0.2 parts of potassium persulfate, 0.2 parts of t-dodecylmercaptan.
and 5 parts of the seed latex obtained in Reference Example 4 were emulsified with 105 parts of ion-exchanged water and polymerized at 60°C for 24 hours with stirring, resulting in a polymerization rate of 94%.
I got the latex.

Next, unreacted monomers were removed by vacuum distillation and the mixture was concentrated to a solid content concentration of 55% and an average particle diameter of 0.
A target latex of 27 μm was obtained. Hereinafter, this latex will be abbreviated as L-2.

Reference Example 6 (same as above) 33 parts of butadiene, 65 parts of styrene, and 2 parts of acrylic acid were combined with 0.5 part of sodium diphenyl ether disulfonate as an emulsifier, 0.2 part of ethylenediaminetetraacetic acid, and potassium persulfate. The control latex was emulsified in 120 parts of ion-exchanged water with 0.2 parts of t-dodecyl mercaptan and 0.5 parts of t-dodecyl mercaptan, and polymerized at 60°C for 13 hours with stirring, resulting in a polymerization rate of 97%. was gotten. Next, unreacted monomers were removed by distillation under reduced pressure and the mixture was concentrated to obtain a desired latex having a solid content concentration of 48% and an average particle size of 0.15 μm. below,
This latex is abbreviated as L'-1.

Examples 1 to 5 and Comparative Examples 1 to 5 Resol emulsion R obtained in Reference Examples 1 and 3
E-1 and RE-1' and the synthetic rubber latexes L-1 and L'-1 obtained in Reference Examples 4 and 6 were blended at the blending ratios shown in Table 1, and blended at 30°C. When examining stability, the results shown in the same table were obtained.

Examples 6-8 Onibi Comparative Examples 6-8 Resol Emulcillin R obtained in Reference Examples 2 and 3
E-2 and RE-1' and the synthetic rubber latexes L-2 and L'-1 obtained in Reference Examples 5 and 6 were
The table shows a comparative study of the coating film performance of each coating film when the coatings were mixed at the proportions shown in the table.

This coating M (made in ¥) was made as follows.

In other words, each formulation was applied using a 0.2× applicator onto a tin plate sanded with sandpaper (roughness 1 m240), left at 25°C for 60 minutes, and then 170°C x 1.5 A cured coating film was obtained by heat treatment for a certain period of time.

In addition, each test regarding each coating film was conducted in the following manner.

Gloss---60 degree specular reflection gloss (JTS K
-5400-6,7) Eriksen - The force of the convex portion was applied gently to the sample, and the pushing length until cracks were generated on the surface was indicated.

゛Impact resistance------ T3 method (JIS K-540
0-6, 13) Adhesion - 1 - Substrate test (J
IS K-5400-6,15) Flexibility------
JIS K-5400-6, 16 Examples 9 to 11 and Comparative Examples 9 to 11 Resole Emulsilon R obtained in Reference Examples 2 and 3
E"2 and RE-x' and the synthetic rubber latexes L-1 and L'-1 obtained in Reference Examples 4 and 6 were mixed into a third
The table shows the results of a test of adhesion to glass fibers using the blending ratios shown in the table.

The adhesion test at this time was conducted as follows.

In other words, using long fiber glass cloth as the glass fiber,
The glass cloth was immersed in a dispersion mixture diluted to a certain concentration for 1 minute to impregnate it with the resin, air-dried, and then dried in a circulating hot-air dryer to harden it to prepare a sample.

Thereafter, adhesive force tests were conducted on each sample, and the costs for each test are as shown below.

Normal tensile strength--The normal tensile strength was measured.

Moisture-resistant tensile car ---- The tensile strength of the sample was measured after it was left at 100% RH 140° C. for 3 days.

The tensile strength was measured as follows.

Measuring machine -------R Shirotsuba - Sub-measuring conditions---Normal tensile strength is 40 kg scale, speed is 180 fin/min, while moisture resistant tensile strength is 20 ktr
On the scale, the speed was set at 180 m/min.

Moisture absorption rate-----The degree of moisture absorption relative to the normal weight after being left at 100% RH and 40C for 3 days is expressed in °C.

Further, the resin adhesion rate was determined as follows.

Examples 12 to 14 and Comparative Examples 12 to 14 Resole Phenol RE-2 and R obtained in Reference Examples 2 and 3
E-1' and the synthetic rubber latexes L-1 and L'-1 obtained in Reference Examples 4 and 6 were blended in the proportions shown in Table 4 to produce a binder for heat-resistant organic synthetic fibers. The suitability of the fibers was compared by measuring the bending resistance of the treated fibers.

The results are summarized in the same table, and the heat-resistant organic fibers [Conex
A polyamide fiber called J (polymetaphenylene isophthalic acid amide manufactured by Kijin Kaisha) was used.

First, to prepare a sample for measuring bending resistance, "Conex" was immersed in a resin solution with a resin concentration of 15% for 1 minute, and the resin adhesion rate after drying and hardening was 10±0.
After adjusting the aperture of the roller so that the aperture was 5%, it was air-dried at room temperature for 1 hour, and then dried and hardened under the conditions shown in the table.

Next, the bending resistance was measured using 2 dll of each resin-treated cloth.
Cut to X1B country size and use the slide method (JIS
L-1079B method).

As is clear from the results in Table 4, when the composition of the present invention is used, it is known that it has a tendency to flexibility and also has excellent heat resistance.

Agent Patent attorney Katsutoshi Takahashi Written amendment to the proceedings Kazuo Wakasugi Director General of the Patent Office 1. Indication of the case Patent Application No. 91301 filed in 1982. 2. Name of the invention: Composition for resin processing 3. 1i Relationship with the case of those who make corrections
B) Dainippon Ink & Chemicals Co., Ltd. Representative: Shigeru Kuni Mura 4, Agent Address: 7-7, Dainippon Ink & Chemicals Co., Ltd., 20 Nihonbashi 3-chome, Chuo-ku, Tokyo 103, Japan Contents of amendment + 11 Page 4 of the specification The statement on line 15, “If indicated by molecule m,” should be corrected to “1 if indicated by molecular weight.”

that's all

Claims (1)

[Claims] Comprising as essential components synthetic rubber latex with an average particle size of 0.2 μm or more and resol type phenolic resin emulsion carbon with an average particle size of 0.3 to 3 μm.
Composition for resin processing.