JPH0578681A - Slipperiness-imparting resin composition - Google Patents

Abstract

PURPOSE:To provide the subject composition containing a copolymer produced by the graft copolymerization of a (meth)acrylate monomer and a polyfunctional monomer to a specific organopolysiloxane and having excellent adhesivity to a substrate such as textile product and low migration tendency. CONSTITUTION:The objective composition having excellent durability contains a graft copolymer produced by the emulsion graftcopolymerization of a mixture of (A) an O/W-type emulsion of 5-95 pts.wt. of an organopolysiloxane of formula I (R<1> to R<3> are 1-20C hydrocarbon group, etc.; Y is radically reactive group, etc.; X is H, etc.; m<=10,000; n>=1) and (B) 95-5 pts. wt. of a monomer mixture composed of (i) 70-99wt.% of a (meth)acrylate monomer of formula II (R<5> is H, etc.; R<6> is 1-18C alkyl, etc.), (ii) 1-20wt.% of a polyfunctional monomer such as ethylenic unsaturated amide and (iii) 0-20wt.% of an ethylenic unsaturated monomer other than the components (i) and (ii) (the sum of the components (i) to (iii) is 100wt.%) in the presence of (C) a radical polymerization initiator.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for imparting surface lubricity to textile products, molded products, foamed products, films, papers and the like.

[0002]

2. Description of the Related Art Conventionally, higher alcohol-based and fatty acid ester-based surfactants have been used as means for imparting lubricity to the surface of various base materials such as textile products, synthetic resin molded products, foamed products, films, paper and wood. A method of coating, impregnating, and kneading silicone oils, waxes, and the like is used, and a method of mixing and using a synthetic resin binder such as an acrylic emulsion in order to improve durability is also used.

[0003]

However, these slipperiness-imparting agents cause bleeding due to lack of adhesion and compatibility with the substrate, resulting in contamination of equipment and other members, poor appearance, and poor adhesion. There are problems in manufacturing and products,
Furthermore, the durability is not satisfactory, and the sliding performance is significantly reduced. The present invention provides a novel lubricity imparting resin composition with improved problems as described above, that is, a novel lubricity imparting resin composition having excellent adhesion to a base material, low migration, and excellent durability. It was made to provide.

[0004]

The lubricity imparting resin composition of the present invention has solved the above-mentioned problems and has the general formula (1):

[Chemical 3] [Wherein R ¹ , R ² and R ³ are one or more groups selected from a monovalent hydrocarbon group having 1 to 20 carbon atoms and a monovalent halogenated hydrocarbon group, Y is one or more groups selected from organic groups containing radically reactive groups and / or SH groups, X is a hydrogen atom, a monovalent lower alkyl group and a formula R ¹ R ² R ⁴ Si A group represented by (R ¹ , R
² is the same as the above, R ⁴ is the same or different group selected from R ¹ and the same group as Y), and m is 1
Positive integer less than or equal to 50,000, n is an integer greater than or equal to 1]
Organopolysiloxane of 5 to 95 parts by weight of oil-in-water emulsion and (B) a) General formula (2)

[Chemical 4] (In the formula, R ⁵ is a hydrogen atom or a methyl group, R ⁶ is a carbon atom 1
To 18 alkyl groups or alkoxy-substituted alkyl groups), and one or more monomers selected from acrylic and / or methacrylic monomers 70 to 9
9% by weight b) Ethylenically unsaturated amide, alkylol- or alkoxyalkyl-substituted compound of ethylenically unsaturated amide, oxirane group-containing ethylenically unsaturated monomer, hydroxyl group-containing ethylenically unsaturated monomer, carboxyl group-containing One or more selected from the group of ethylenically unsaturated monomers, complete ester of polyhydric alcohol and acrylic acid or methacrylic acid, diallyl ester of dibasic acid, allyl acrylate, allyl methacrylate and divinylbenzene 1 to 20 wt% of polyfunctional monomer c) Mixed monomer [a) to 0 to 20 wt% of one or more ethylenically unsaturated monomers other than the above a) and b) A total of 100% by weight of c)] 95 to 5 parts by weight, and a graph obtained by emulsion-grafting copolymerization in the presence of a radical polymerization initiator. It is characterized in that comprises a copolymer.

As a result of intensive studies for solving the above problems, the present inventors have found that a copolymer obtained by graft-copolymerizing an acrylic and / or methacrylic monomer and a polyfunctional monomer onto an organopolysiloxane is used. The present invention has been accomplished by finding that the resin composition containing the resin has excellent properties. The present invention will be described in detail below.

The above-mentioned component (A), organopolysiloxane, has the general formula (1)

[Chemical 5] And R ¹ , R ² and R ³ are carbon numbers exemplified by alkyl groups such as methyl group, ethyl group, propyl group and butyl group, aryl groups such as phenyl group, tolyl group, xylyl group and naphthyl group. 1 to 20 monovalent hydrocarbon groups and groups in which some or all of the hydrogen atoms bonded to the carbon atoms of these groups are substituted with halogen atoms, and X is a hydrogen atom, a methyl group, an ethyl group. , Lower alkyl groups having 1 to 5 carbon atoms such as propyl group, butyl group, pentyl group and R ¹ R ²
A triorganosilyl group represented by R ⁴ Si (R ¹ and R ² are the same as described above, R ⁴ is the same as R ¹ or Y), and Y is a vinyl group, an allyl group, or γ-acryloxy. It is selected from radical-reactive groups exemplified by propyl group, γ-methacryloxypropyl group, γ-mercaptopropyl group and SH group-containing organic group. m is 10,
Is a positive integer of 000 or less, and n is an integer of 1 or more, preferably 200 <m <8,000, 1 <n <50
It should be in the range of 0.

The emulsion of the component (A) may be produced by a known method. One of the methods is to use, as raw materials, a cyclic low molecular weight organosiloxane such as octamethylcyclotetrasiloxane and a radical-reactive group or SH group. Using the dialkoxysilane compound contained therein and / or its hydrolyzate, polymerization is carried out in the presence of a strong alkaline catalyst or a strong acid catalyst to obtain a high molecular weight organopolysiloxane, which is then dissolved in water in the presence of a suitable emulsifier. This is because it is emulsified and dispersed in.

Another method is, for example, a dialkoxysilane compound containing the above-mentioned low molecular weight organosiloxane as a raw material and a radical reactive group or SH group, and / or
Or a hydrolyzate thereof and emulsion-polymerized in water in the presence of a sulfonic acid type surfactant and / or a sulfuric acid ester type surfactant.

In the case of this emulsion polymerization, the same raw materials are used, and after emulsion-dispersion in water with a cationic surfactant such as alkyltrimethylammonium chloride or alkylbenzylammonium chloride,
It is also possible to polymerize by adding a suitable amount of a strong alkaline substance such as potassium hydroxide or sodium hydroxide.

The above-mentioned sulfonic acid type surfactant and sulfuric acid ester type surfactant serve both as an emulsifier and a polymerization catalyst.

[Chemical 6]

[Chemical 7]

[Chemical 8]

[Chemical 9]

[Chemical 10] C ₈ H ₁₇ (OC ₂ H ₄ ) ₂ OSO ₃ H, C ₁₀ H ₂₁ (OC
₂ H ₄ ) ₂ OSO ₃ H, sodium lauryl sulfate, sodium polyoxyethylene dodecylphenyl sulfate and the like are exemplified. Of these, the sulfate ester salts are converted into corresponding acids by contacting with a cation exchange resin after the completion of emulsification, and function as a polymerization catalyst. After the completion of emulsion polymerization, the acid-form surfactant may be neutralized to eliminate the catalytic activity.

Further, as the cationic emulsifier, the quaternary ammonium salt type as described above is mainly used, and after the completion of emulsion polymerization, the basic type surfactant may be neutralized to eliminate the catalytic activity. ..

Furthermore, the size of the molecular weight of the organopolysiloxane can be adjusted by the temperature during the aging carried out after the emulsion polymerization. Therefore, the aging temperature may be set according to the desired physical properties.

Next, the component (B) will be described. This is a mixture of polymerizable monomers for graft-copolymerizing with the organopolysiloxane of the component (A) described above. It is composed of three components.

Component (a) has the general formula (2)

[Chemical 11] (In the formula, R ⁵ is hydrogen or a methyl group, and R ⁶ has 1 to 1 carbon atoms.
(Meth) acrylic monomer represented by the alkyl group or alkoxy-substituted alkyl group of 8 [wherein the expression (meth) acrylic collectively represents both acrylic and methacrylic, and the same applies hereinafter. ], And methyl (meth) acrylate, ethyl (meth) acrylate,
Propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, Alkyl (meth) acrylates such as stearyl (meth) acrylate and alkoxyalkyl (meth) acrylates such as methoxyethyl (meth) acrylate and butoxyethyl (meth) acrylate are exemplified, and one or more of these are used in combination. To be done.

The amount of the component (a) is 70 in the component (B).
If it is less than 5% by weight, the properties of (meth) acrylic, especially the properties such as film forming property, film strength, and adhesion to a substrate, are insufficient.

The component (b) is a polyfunctional monomer, and is (meth) as an ethylenically unsaturated amide, an alkylol- or alkoxyalkyl-substituted compound of the ethylenically unsaturated amide.
Glycidyl (meth) acrylate as an oxirane group-containing unsaturated monomer such as acrylamide, diacetone (meth) acrylamide, N-methylol (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide , 2-hydroxyethyl (meth) acrylate as a hydroxyl group-containing unsaturated monomer, such as glycidyl allyl ether,
As a carboxyl group-containing ethylenically unsaturated monomer such as 2-hydroxypropyl (meth) acrylate (meth)
Acrylic acid, maleic anhydride, crotonic acid, itaconic acid, etc. As a complete ester of polyhydric alcohol and (meth) acrylic acid, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) Examples thereof include acrylate, allyl (meth) acrylate, and divinylbenzene.

These polyfunctional monomers increase the adhesion to the base material and give the film durability and solvent resistance. If the amount of the component (B) is increased, the desired properties are improved, but if the amount is too large, the coating becomes hard and cracking occurs and the water resistance decreases. It is necessary to set the content to 20% by weight.

The component (c) is another ethylenically unsaturated monomer, and the component (B) is used in an amount of 0 to 20% by weight in order to impart a touch, durability and the like which cannot be exhibited only by the components a) and b). However, if it exceeds 20% by weight, the characteristics of acrylic resin will be impaired. Examples of such a monomer include styrene, α-methylstyrene, acrylonitrile, vinyl chloride, vinylidene chloride, vinyl acetate, vinyl propionate, and vinyl versatate.

Regarding the ratio of the component (A) to the component (B), when the amount of the component (A) is less than 5 parts by weight, the effect of imparting lubricity unique to the organopolysiloxane is poor, and the effect of reducing frictional and squeaking noises is also obtained. When the amount exceeds 95 parts by weight, the adhesion to the substrate is poor and the durability is impaired, and moreover, a sticky feeling is produced, which is not practical.

The emulsion graft copolymerization of the components (A) and (B) may be carried out by a known emulsion polymerization method using an ordinary radical initiator. As the radical initiator used here, persulfates such as potassium persulfate and ammonium persulfate, hydrogen peroxide solution, t-butyl hydroperoxide,
Water-soluble type such as azobisamidinopropane hydrochloride,
Benzoyl peroxide, cumene hydroperoxide, dibutyl peroxide, diisopropyl peroxydicarbonate, cumyl peroxy neodecanoate,
Examples include oil-soluble types such as cumyl peroxy octoate and azobisisobutyronitrile. Furthermore, if necessary, a redox system in which a reducing agent such as acidic sodium sulfite, Rongalit, L-ascorbic acid, saccharides, amines is used together can be used.

At the time of emulsion graft copolymerization, since the emulsifier is contained in the emulsion of the component (A), it is not always necessary to newly use the emulsifier, but prevention of coagulation during the polymerization and formation of an emulsion can be performed. If necessary, a necessary amount of emulsifier may be added to improve stability. Examples of the emulsifier used here include anionic emulsifiers such as alkyl or alkylallyl sulfates or sulfonates and alkylallyl succinates, cationic emulsifiers such as alkyltrimethylammonium chloride and alkylbenzylammonium chloride, and polyoxyethylene. Nonionic emulsifiers such as alkyl ethers and polyoxyethylene carboxylic acid esters are suitable.

If necessary, the resin composition for imparting lubricity of the present invention may contain other resin emulsions such as fluorine-based emulsions, silicone-based emulsions, styrene-based emulsions, acrylic ester-based emulsions, rubber-based emulsions and glyoxal-based emulsions. Resins and the like can be arbitrarily mixed, and various additives such as flame retardants, fillers, and colorants can be added as necessary.

When it is necessary to adjust the viscosity of the emulsion, a suitable amount of polyvinyl alcohol, gelatin, methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and other cellulose derivatives, xanthan gum, sodium polyacrylate, polyacrylamide and the like are added. do it.

The slipperiness-imparting resin composition of the present invention is used as a fiber product,
As a method for treating the surface of various base materials such as synthetic resin molded products, foamed products, films, papers and woods, usual treatment methods such as impregnation treatment, spray treatment and coating treatment are used.

[0025]

EXAMPLES The present invention will be specifically described based on examples.
All parts in the examples are parts by weight, and% is% by weight.

(Preparation of Organopolysiloxane Emulsion) Octamethylcyclotetrasiloxane 1500
Parts, methacryloxypropyl methyl siloxane 3.8
And 1500 parts of pure water are mixed, and 15 parts of sodium lauryl sulfate and 10 parts of dodecylbenzenesulfonic acid are added to the mixture, and the mixture is stirred with a homomixer to emulsify and then passed through a homogenizer with a pressure of 3000 psi twice to stabilize. I made a nice emulsion. Then, after heating this at 70 ° C for 12 hours, cooling to 25 ° C and aging for 24 hours, the pH of this emulsion was adjusted to 7 with sodium carbonate, nitrogen gas was blown for 4 hours, and steam distillation was performed. The volatile siloxane was distilled off, and then pure water was added to adjust the nonvolatile content to 45%, and the methacrylic group was added at 0.1 mol%.
An emulsion of the containing organopolysiloxane was obtained. (Hereinafter, this is abbreviated as E-1.) Also, as shown in Table 1, organopolysiloxane emulsions E-2 to E-2 are prepared in the same manner as in E-1, except that the type and amount of siloxane and the aging conditions are changed. E-4 was obtained.

[0027]

[Table 1]

(Production of Organopolysiloxane / Acrylic Graft Copolymer Emulsion) The organopolysiloxane emulsion E-1 obtained above was placed in a reaction vessel equipped with a stirrer, a condenser, a thermometer and a nitrogen gas inlet.
After charging 556 parts (organopolysiloxane content 250 parts) and pure water 444 parts and adjusting the inside of the container to 30 ° C. under a nitrogen gas stream, t-butyl hydroperoxide 1.0.
Parts, 0.5 part of L-ascorbic acid and 0.002 part of ferrous sulfate heptahydrate, and then while maintaining the temperature inside the container at 30 ° C., butyl acrylate 234.7 parts, acrylic acid 7.5 parts And a mixture of 3.8 parts of methacrylic acid, and N-
40 parts of a 10% aqueous solution of methylolacrylamide was added to 3 parts.
The reaction mixture was added dropwise over a period of time, and after completion of the addition, stirring was continued for 1 hour to complete the reaction. The resulting copolymer emulsion (hereinafter abbreviated as P-1) had a solid content concentration of 39.8%. In the same manner as described above, copolymerized emulsions P-2 to P having a solid content concentration of 39 to 40% were copolymerized by the types and amounts of the organopolysiloxane emulsions and (meth) acrylic monomers shown in Table 2 and the like. -4 was obtained.

[0029]

[Table 2]

(Preparation and Evaluation of Lubricity-Providing Resin Composition) Using the copolymer emulsions P-1 to P-4 obtained above, a lubricity-imparting resin composition (treatment liquid) was prepared and its performance was evaluated. .. The performance was evaluated as follows. (Sliding property) Evaluation was performed by touch. Performance display: Good ○ to △ to × to × × Poor (Transition) Evaluated by touch. Performance indication: Less transfer to hand ○ ～ △ ～ × ～ ×× More transfer to hand (friction noise) Rubbing the surface of the treated cloth with untreated polyester cloth under a certain load, and hearing the loudness at that time The evaluation was made according to. Performance display: low friction noise ○ ～ △ ～ × high friction noise

The washing treatment and heat treatment shown in Tables 3 to 5 were carried out as follows. (Washing treatment) Using a household washing machine, using Top [trade name of Lion Co., Ltd.] as a detergent, a concentration of 2 g / liter,
After stirring for 5 minutes under conditions of a bath ratio of 1:30 and a temperature of 40 ° C., washing with water, dehydration, and drying at room temperature were performed.
This was repeated 10 times. (Heat treatment) 3 in a soaking hot air dryer with an ambient temperature of 150 ° C
It was left for 00 hours.

Example 1 and Comparative Example 1 A treatment liquid was prepared using the copolymer emulsion P-1 and impregnated into a polyester twill fabric to evaluate its performance.
The treatment was carried out by diluting 10 parts of P-1 with 90 parts of water as a treatment liquid, impregnating this with a polyester twill fabric, and squeezing the excess liquid so that the adhesion amount was about 20 g / m ² in Dry. And then pre-dry at 120 ° C for 3 minutes, then 15
It was performed by heating and curing at 0 ° C./2 minutes. For comparison, instead of P-1, 40 parts of VINYBLANC 2632 [manufactured by Nisshin Chemical Industry Co., Ltd., trade name of polyacrylic acid ester emulsion, solid content 45%] and PORON MF-14 [manufactured by Shin-Etsu Chemical Industry Co., Ltd.] Amino silicone emulsion product name,
A mixture of 60 parts of solid content 30%] was used and treated in the same manner as above. The evaluation results are shown in Table 3.

[0033]

[Table 3]

Example 2 and Comparative Example 2 A treatment liquid was prepared using the copolymer emulsion P-2, and the nylon taffeta was coated to evaluate the performance. As for the treatment, the viscosity of P-2 was about 30,000 cp (B type, 20 ° C., 6 rp) with a sodium polyacrylate thickener.
m) thickened to about 2 with a bar coater in Dry
The coating was performed so that the coating amount was 0 g / m ² , pre-dried at 120 ° C. for 5 minutes, and further heated and cured at 150 ° C. for 2 minutes. For comparison, instead of P-2, Vinibrand 2
598 [Nissin Chemical Industry Co., Ltd. polyacrylic ester emulsion trade name, solid content 45%] 40 parts and Polon M
A mixture of 60 parts of F-17 [trade name of dimethyl silicone emulsion manufactured by Shin-Etsu Chemical Co., Ltd., solid content: 30%] was used and treated in the same manner as above. The evaluation results are shown in Table 4.

[0035]

[Table 4]

Example 3 and Comparative Example 3 A treatment liquid was prepared using the copolymer emulsion P-3, and a polyester nonwoven fabric was coated and evaluated for performance. As for the treatment, the viscosity of P-3 was about 50,000 cp (B type, 20 ° C., 6 rp) with a sodium polyacrylate thickener.
m) thickened to about 4 with a bar coater
It was applied by coating so as to be 0 g / m ² and dried at 130 ° C./10 minutes. For comparison, in place of P-3, VINYBLANC 2632 [polyacrylic acid ester emulsion manufactured by Nisshin Chemical Industry Co., Ltd., trade name, solid content 45%] 6
A mixture of 0 parts and 40 parts of PORON MF-14 [Shin-Etsu Chemical Co., Ltd., aminosilicone emulsion trade name, solid content 30%] was used and treated in the same manner as above. The evaluation results are shown in Table 5.

[0037]

[Table 5]

Example 4, Comparative Example 4 A treatment liquid was prepared using the copolymer emulsion P-4, and the urethane foam was subjected to a spray treatment for performance evaluation.
The treatment was carried out by diluting 50 parts of P-4 with 50 parts of water by spraying about 150 g / m ^{2 and then} drying at 120 ° C. for 5 minutes. For comparison, in place of P-4, VINYBRAN 2598 [NISSHIN CHEMICAL INDUSTRIES, LTD. Product name polyacrylic acid ester emulsion, solid content 45%] 60
And 40 parts of PORON MF-17 [trade name of dimethyl silicone emulsion manufactured by Shin-Etsu Chemical Co., Ltd., solid content: 30%] was used and treated in the same manner as above. The evaluation results are as shown in Table 6.

[0039]

[Table 6]

Reference Example 1 When a seat belt of a vehicle was treated with the composition of the present invention, the slip property of the belt was remarkably improved, and the handling of the belt during loading / unloading was extremely smooth. It became so.

Reference Example 2 When a vehicle seat was produced, urethane foam was treated with the composition of the present invention, and the slipperiness of the foam surface was increased, so that the workability when mounting a skin material was improved. , It was effective in shortening the time.

Reference Example 3 When a vehicle seat was manufactured, urethane foam was treated with the composition of the present invention, and the frictional resistance between the foam surface and the seat frame was reduced, which was caused by the contact during driving. Offensive fricatives have been reduced.

Reference Example 4 When the inner surface of the paper used for packaging was treated with the composition of the present invention, slipperiness was imparted and the contents could be easily taken out.

Reference Example 5 When the composition of the present invention was applied to a sillboard such as sliding doors, sliding doors and shoji screens, sliding when opening and closing sliding doors was improved and squeak noise was eliminated.

[0045]

Industrial Applicability According to the present invention, there is provided a novel lubricity imparting resin composition having excellent adhesion to various substrates, low migration and excellent durability. This slipperiness-imparting resin composition has excellent properties such as excellent slipperiness and low friction noise.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location C10M 107: 04) C10N 50:02

Claims (1)

[Claims] 1. (A) General formula (1): [Wherein R ¹ , R ² and R ³ are one or more groups selected from a monovalent hydrocarbon group having 1 to 20 carbon atoms and a monovalent halogenated hydrocarbon group, Y is one or more groups selected from organic groups containing radically reactive groups and / or SH groups, X is a hydrogen atom, a monovalent lower alkyl group and a formula R ¹ R ² R ⁴ Si A group represented by (R ¹ , R
² is the same as the above, R ⁴ is the same or different group selected from R ¹ and the same group as Y), and m is 1
Positive integer less than or equal to 50,000, n is an integer greater than or equal to 1]
Organopolysiloxane represented by the formula: 5 to 95 parts by weight of oil-in-water emulsion and (B) a) General formula (2) (In the formula, R ⁵ is a hydrogen atom or a methyl group, R ⁶ is a carbon atom 1
To 18 alkyl groups or alkoxy-substituted alkyl groups), and one or more monomers selected from acrylic and / or methacrylic monomers 70 to 9
9% by weight b) Ethylenically unsaturated amide, alkylol- or alkoxyalkyl-substituted compound of ethylenically unsaturated amide, oxirane group-containing ethylenically unsaturated monomer, hydroxyl group-containing ethylenically unsaturated monomer, carboxyl group-containing One or more selected from the group consisting of ethylenically unsaturated monomers, complete esters of polyhydric alcohols with acrylic acid or methacrylic acid, diallyl esters of dibasic acids, allyl acrylates, allyl methacrylates and divinylbenzene. 1 to 20 wt% of polyfunctional monomer c) Mixed monomer [a) to 0 to 20 wt% of one or more ethylenically unsaturated monomers other than a) and b) above A total of 100% by weight of C)] 95 to 5 parts by weight of a mixture obtained by emulsion graft copolymerization in the presence of a radical polymerization initiator. Slipping resin composition characterized by containing the copolymer.