JP2006008764A - Water-based resin dispersion for processing construction material decorative paper - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a water-based resin dispersion for processing construction material decorative paper good in film formability and solvent resistance, excellent in mechanical stability, chemical stability and storage stability when used as a binder resin for construction material decorative paper in particular, and also excellent in the hot roll blocking resistance of a processed base obtained by processing and in processed paper's interpaper strength, and to provide such a processed base obtained using the resin dispersion. <P>SOLUTION: The water-based resin dispersion is obtained by emulsion copolymerization in an aqueous medium between 15-25 pts.wt. of (A) a cyano-containing ethylenically unsaturated monomer, 5-40 pts.wt. of (B) styrene, 2-8 pts.wt. of (C) an amido-containing ethylenically unsaturated monomer, 0.1-1 pt.wt. of (D) a vinyl-containing silane coupling agent and 26-77.9 pts.wt. of (E) another ethylenically unsaturated monomer. The total amount of these monomers is based on 100 pts.wt. of the solid content of this dispersion. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

The present invention relates to an aqueous resin dispersion for processing decorative paper for building materials, and a processed substrate using the same.
More specifically, it has excellent film-forming properties and solvent resistance, and when used as a paper processing agent, particularly as a binder resin for decorative paper for building materials, it has excellent mechanical stability, chemical stability, and storage stability, and it is processed. The processing base material obtained by this is related with the heat-resistant roll blocking property and the water-based resin dispersion for processing decorative paper, and the processing base material using the same.

As an environmentally friendly material that can be recycled, the demand for paper is increasing year by year. Recently, paper has been gaining attention as an alternative material for plastics and is gradually being put into practical use in the fields where plastics have been used. Accordingly, it has been demanded to improve the properties of paper suitable for various uses.
However, the pulp that is the main raw material of paper has been decreasing year by year, and the situation has been that the raw materials with short fiber length and recycled paper that have not been used in the past must be used as raw materials for paper. There is a problem that when such a low-quality pulp raw material is used, there is a problem in that the strength between the papers is lowered.

In addition, the resin-impregnated paper for building material decorative paper impregnated with the aqueous resin dispersion is subjected to calendering after drying, but the processing temperature at that time is usually as high as 120 ° C to 250 ° C. In order to prevent blocking, it is necessary to add a crosslinking agent.
However, conventionally, when a cross-linking agent is used to prevent blocking to the hot roll, blocking to the hot roll is improved, but there is a problem that strength between papers is lowered.

Conventionally, various proposals have been made to improve such a problem.
Since the amide group of acrylamide forms a hydrogen bond with a hydroxyl group in the cellulose molecule of paper, it is known that a processing agent containing a large amount of acrylamide improves the inter-paper strength, and there are many proposals using this.
For example, for impregnated paper obtained by emulsion polymerization of a radically polymerizable monomer mixture containing N-methylol (meth) acrylamide, (meth) acrylamide and itaconic acid using a nonionic emulsifier and / or an anionic emulsifier. An emulsion polymerization composition (Patent Document 1) has been proposed and is said to be effective in improving the tensile strength, folding strength, and gum-up resistance of paper.
However, in such an emulsion-polymerized composition for impregnated paper, the acrylic emulsion obtained by copolymerizing the obtained N-methylol (meth) acrylamide is capable of exhibiting some inter-paper strength and solvent resistance by crosslinking. On the contrary, harmful formalin was generated and there was a problem in practical use.

Further, a polymerizable monomer comprising an aliphatic conjugated diene monomer, an ethylenically unsaturated acid monomer, and other copolymerizable monomers in the presence of a water-soluble polymer containing 60% by weight or more of acrylamide. An aqueous polymer composition (Patent Document 2) that polymerizes a monomer mixture to produce polymer fine particles has been proposed, and mechanical and chemical stability is improved by complexing a copolymer latex (polymer fine particles). A good aqueous polymer composition can be provided, and surface strength, internal strength, printability, water resistance (size), etc. are said to be good.
However, in such an aqueous polymer composition, since the content of acrylamide is high, the viscosity of the aqueous resin dispersion becomes too high, making it difficult to achieve a high solid content concentration, and the reaction is in two stages. There was a problem that time was long and uneconomical.

Furthermore, as other crosslinking agents, oxazoline-based, epoxy-based, isocyanate-based crosslinking agents and the like are known.
However, when these cross-linking agents are used, the water resistance and heat-resistant roll blocking properties are improved, but there arises a problem that the inter-paper strength and the printability are lowered. Moreover, since a reaction proceeds at room temperature, a crosslinking agent such as oxazoline and isocyanate needs to be used in two liquids, which is not preferable in terms of cost and workability. On the other hand, glycidyl methacrylate and phthalic acid diallyl ester are effective in improving the heat-resistant roll blocking property, but there is a problem that the strength between papers is remarkably lowered.

JP-A-9-279085 Japanese Patent Laid-Open No. 10-36458

  The object of the present invention is excellent in film-forming property and solvent resistance, and when used as a paper processing agent, particularly as a binder resin for decorative paper for building materials, is excellent in mechanical stability, chemical stability and storage stability. The processing base material obtained by processing is to provide a heat-resistant roll blocking property and a water base resin dispersion for processing decorative paper for processing paper having excellent paper-to-paper strength, and a processing base material using the same.

  As a result of intensive studies to solve the above problems, the present inventors have included a hydrophobic monomer, in particular, styrene in a specific range, whereby an amide group-containing ethylenically unsaturated monomer that is a hydrophilic monomer. Is localized on the surface of the aqueous resin dispersion particles, and the strength between papers can be greatly improved with a small amount of an amide group-containing ethylenically unsaturated monomer. And found that heat-resistant roll blocking properties can be improved without reducing the inter-paper strength when a vinyl group-containing silane coupling agent is used in a specific range, and the present invention has been completed. It came to do.

  That is, the present invention provides an aqueous resin dispersion having a solid content of 100 parts by weight, 15 to 25 parts by weight of a cyano group-containing ethylenically unsaturated monomer (A), 5 to 40 parts by weight of styrene (B), Amide group-containing ethylenically unsaturated monomer (C) 2-8 parts by weight, vinyl group-containing silane coupling agent (D) 0.1-1 part by weight, and other ethylenically unsaturated monomers ( E) Provided is an aqueous resin dispersion for processing decorative paper for building materials, comprising 26 to 77.9 parts by weight and emulsion-polymerized in an aqueous medium.

  Further, the present invention provides a cyano group-containing ethylenically unsaturated monomer (A) 15 to 25 parts by weight, a styrene (B) 5 to 40 parts by weight, 2-8 parts by weight of a saturated monomer (C), 0.1-1 part by weight of a vinyl group-containing silane coupling agent (D), and 26-77. What is provided is a processed base material characterized by being obtained using an aqueous resin dispersion for processing decorative paper for building materials, comprising 9 parts by weight and emulsion-polymerized in an aqueous medium It is.

The aqueous resin dispersion for processing decorative paper of the present invention has excellent film-forming properties and solvent resistance, and is mechanically stable and chemically stable when used as a paper processing agent, particularly as a binder resin for decorative paper for building materials. The processing base material obtained by processing is excellent in heat-resistant roll blocking property and inter-paper strength of processed paper.
The processed base material using the aqueous resin dispersion for building material decorative paper processing of the present invention has excellent paper-to-paper strength and printability, and there is no process trouble due to blocking by ink back-through and hot roll blocking at the time of calendar treatment. It is excellent in productivity and extremely useful as a processed substrate.

The matters necessary for carrying out the present invention are described below.
The aqueous resin dispersion for processing decorative paper for building materials of the present invention includes, as essential components, a cyano group-containing ethylenically unsaturated monomer (A), styrene (B), and an amide group-containing ethylenically unsaturated monomer. An aqueous solution obtained by emulsion polymerization of a mixture of a radically polymerizable monomer containing (C), a vinyl group-containing silane coupling agent (D), and another ethylenically unsaturated monomer (E) in an aqueous medium. It is a resin dispersion.

  Examples of the cyano group-containing ethylenically unsaturated monomer (A) used in the emulsion polymerization of the aqueous resin dispersion for processing decorative paper of the present invention include, for example, acrylonitrile, methacrylonitrile, crotonnitrile, and α-chloroacrylonitrile. In order to improve printability, (meth) acrylonitrile is preferable, and these may be used alone or in combination of two or more.

The amount of the cyano group-containing ethylenically unsaturated monomer (A) used is preferably in the range of 15 to 25 parts by weight, more preferably 15 to 15 parts by weight with respect to 100 parts by weight of the solid content of the aqueous resin dispersion. The range is 20 parts by weight.
If the amount of the cyano group-containing ethylenically unsaturated monomer (A) is within the range, the printability is improved, there is no blocking due to ink back-through and the like, and the reactivity is excellent. When styrene (B) is used in combination as a polymerizable unsaturated monomer, the emulsion polymerization can proceed normally without significant increase in viscosity.

  In the aqueous resin dispersion for processing decorative paper for building materials of the present invention, the amount of styrene (B) used is preferably in the range of 5 to 40 parts by weight with respect to 100 parts by weight of the solid content of the aqueous resin dispersion. More preferably, it is the range of 5-30 weight part, More preferably, it is the range of 10-30 weight part. If the amount of the styrene (B) used is within such a range, the amide group-containing ethylenically unsaturated monomer (C) can be localized on the particle surface of the aqueous resin dispersion, and the strength between papers can be improved. Excellent texture.

Examples of the amide group-containing ethylenically unsaturated monomer (C) used in the emulsion polymerization of the aqueous resin dispersion for processing decorative paper of the present invention include, for example, (meth) acrylamide, N-methylol (meth) acrylamide. , N-butoxymethylacrylamide, diacetoneacrylamide, etc., may be used alone or in combination of two or more. Among these, (meth) acrylamide is preferable because it does not generate formaldehyde harmful to the human body.
In the present invention, (meth) acrylamide means methacrylamide and / or acrylamide unless otherwise specified.

  The amount of the amide group-containing ethylenically unsaturated monomer (C) used is preferably in the range of 2-8 parts by weight, more preferably 3-8 parts by weight with respect to 100 parts by weight of the solid content of the aqueous resin dispersion. It is in the range of 5% by weight. If the amount of the amide group-containing ethylenically unsaturated monomer (C) is within such a range, the viscosity of the resulting aqueous resin dispersion will be in a practically appropriate range, and workability in the paper processing process will be improved. In addition to being excellent, it also has excellent printability and inter-paper strength after processing.

  Further, the vinyl group-containing silane coupling agent (D) used in the emulsion polymerization of the aqueous resin dispersion for building material decorative paper processing of the present invention is not particularly limited, and examples thereof include vinyltrimethoxysilane, vinyltriethoxysilane, Vinyltris (βmethoxyethoxy) silane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxylane, etc. May be used alone or in combination of two or more.

  The amount of the vinyl group-containing silane coupling agent (D) used is preferably in the range of 0.1 to 1 part by weight, more preferably 0.2 to 100 parts by weight of the solid content of the aqueous resin dispersion. It is in the range of -0.8% by weight. If the use amount of the vinyl group-containing silane coupling agent (D) is within such a range, the use of a small amount is excellent in the effect of improving the heat-resistant roll blocking property, which is advantageous in terms of cost.

  Furthermore, the other ethylenically unsaturated monomer (E) used in the emulsion polymerization of the aqueous resin dispersion for processing building paper of the present invention is the above-described cyano group-containing ethylenically unsaturated monomer (A ), Styrene (B), amide group-containing ethylenically unsaturated monomer (C), and vinyl group-containing silane coupling agent (D), and other ethylenically unsaturated monomers copolymerizable Although not specifically limited, for example, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, hexyl acrylate, hexyl methacrylate, acrylic acid Heptyl, heptyl methacrylate, octyl acrylate, octyl methacrylate, octadecyl acrylate, methacrylate Acrylic acid alkyl esters and methacrylic acid alkyl esters exemplified by tadecyl, aliphatic conjugated diene monomers such as 1,2-butadiene, 1,3-butadiene, isoprene, chloroprene, α-methylstyrene, vinyltoluene, Ethylenically unsaturated aromatic monomers such as chlorostyrene, 2,4-dibromostyrene, acrylic acid, methacrylic acid, crotonic acid, maleic acid and its anhydride, fumaric acid, itaconic acid and unsaturated dicarboxylic acid Monoalkyl esters, for example, vinyl esters such as ethylenically unsaturated carboxylic acids such as monomethyl maleate, monoethyl fumarate, mononormal butyl itaconate, vinyl acetate, vinyl propionate, vinylidene chloride such as vinylidene chloride, vinylidene bromide, etc. Halide, acrylic acid Ethylenically unsaturated carboxylic acids such as hydroxyalkyl esters of ethylenically unsaturated carboxylic acids such as 2-hydroxyethyl, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, etc. These monomers include radically polymerizable monomers such as glycidyl esters, and these may be used alone or in combination of two or more.

  The amount of the other ethylenically unsaturated monomer (E) used is as described above with respect to 100 parts by weight of the solid content of the aqueous resin dispersion, and the cyano group-containing ethylenically unsaturated monomer (A) and styrene. (B), amide group-containing ethylenically unsaturated monomer (C), and vinyl group-containing silane coupling agent (D) used are the remaining parts by weight, that is, 26 to 77. The range is 9 parts by weight.

  The aqueous resin dispersion for processing decorative paper for building materials of the present invention is not particularly specified in its structure, but according to analysis using a surface analyzer such as X-ray photoelectron spectroscopy (X-ray photoelectron spectroscopy), Bias is observed in the distribution of amide groups in the resin dispersion of the present invention, that is, a small amount of amide group-containing ethylenically unsaturated monomer used by distributing a large amount of amide groups on the surface of the resin dispersion particles. However, the inter-sheet strength of the processed paper can be improved as never before.

As a method for producing the aqueous resin dispersion for paper processing of the present invention, a known and commonly used method can be adopted, and there is no particular limitation. Usually, the polymerization reaction is carried out by keeping the polymerization solution in a predetermined temperature range in the presence of a radical polymerization initiator. Can be done.
As the polymerization method, for example, a batch polymerization method in which all the monomers to be used are charged in a reaction vessel and polymerized, or a half batch polymerization method in which a part of the monomer is continuously added during the polymerization reaction, etc. Any method may be used without any particular limitation.
It is not necessary to maintain the same temperature during the polymerization reaction, and the polymerization may be performed while heating or gradually heating while appropriately adjusting the temperature as the polymerization reaction proceeds.
The polymerization temperature varies depending on the type of monomer used and the polymerization initiator, and is not particularly limited. However, in the case of a single initiator, it is usually in the range of 30 to 100 ° C. In the case of a redox polymerization initiator In the case of sequential addition, the temperature is in the range of 30 to 95 ° C., and in the case of batch polymerization, if the reaction kettle is a high-pressure closed system, even if it exceeds 100 ° C. within a range where there is no safety problem. I do not care.
The atmosphere in the polymerization reactor is not particularly limited, but it is preferably replaced with an inert gas such as nitrogen gas before the start of the reaction in order to carry out the polymerization reaction quickly.
The polymerization time is not particularly limited, but is usually 1 to 40 hours.

Examples of the emulsifier used in the production of the aqueous resin dispersion for paper processing of the present invention include generally available anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants. May be used as long as the object of the present invention is not impaired, and there is no particular limitation.
Examples of the anionic emulsifier include sulfates of higher alcohols, alkylbenzene sulfonates, polyoxyethylene alkylphenyl sulfonates, and the like. These may be used alone or in combination of two or more.
Examples of the nonionic emulsifier include polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene-polyoxypropylene block copolymer, and the like. These may be used alone or in combination of two or more. May be.
Examples of the cationic emulsifier include alkylammonium salts such as dodecyl ammonium chloride. These may be used alone or in combination of two or more.
Examples of the amphoteric emulsifier include betaine ester type emulsifiers, and these may be used alone or in combination of two or more.
Furthermore, an emulsifier having a polymerizable unsaturated group in the molecule generally called “reactive emulsifier” can also be used. Examples of reactive emulsifiers that can be used in the present invention include "Latemul S-180"(trademark; manufactured by Kao Corporation) having a sulfonic acid group and a salt thereof, and "Eleminol JS-2, RS-30"[trademark; Sanyo Kasei Kogyo Co., Ltd.] or the like; or “Aqualon KH-05, KH-10” [trademark; Daiichi Kogyo Seiyaku Co., Ltd.] having sulfate groups and salts thereof, “Adekaria Soap SE-10, SE” -20 ”[trademark; manufactured by Asahi Denka Kogyo Co., Ltd.], etc .; or“ New Frontier A-229E ”having a phosphate group (trademark; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), etc .; or nonionic hydrophilic groups “AQUALON RN-10, RN-20, RN-30, RN-50” (trademark; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and the like are included, and these may be used alone or in combination of two or more. Good.

As the polymerization initiator used in the emulsion polymerization, radical polymerization initiators are used. For example, persulfates such as potassium persulfate, sodium persulfate, ammonium persulfate, benzoyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide. Organic peroxides such as oxides, hydrogen peroxide, etc. are mentioned, radical polymerization is carried out using only these peroxides, or metal salts of the peroxide and ascorbic acid, formaldehyde sulfoxylate, Polymerization can also be achieved by a redox polymerization initiator system in combination with a reducing agent such as sodium thiosulfate, sodium bisulfite, ferric chloride, etc., and 4,4′-azobis (4-cyanovaleric acid), 2, It is also possible to use an azo initiator such as 2′-azobis (2-amidinopropane) dihydrochloride, It may be a good combination of two or more types may be used.
Among the polymerization initiators, examples of the organic peroxides include diacyl peroxides such as benzoyl peroxide, lauroyl peroxide, decanoyl peroxide, and dialkyls such as t-butylcumyl peroxide and dicumyl peroxide. Peroxyesters such as peroxides, t-butyl peroxylaurate, t-butyl peroxybenzoate, hydroperoxides such as cumene hydroperoxide, paramentane hydroperoxide, t-butyl hydroperoxide, etc. 1 type, or 2 or more types of these can be used.
Among the polymerization initiators, examples of the reducing organic compound include ascorbic acid and salts thereof, erythorbic acid and salts thereof, tartaric acid and salts thereof, citric acid and salts thereof, and metal salts of formaldehyde sulfoxylate. In combination with the above organic peroxides, one or a mixture of two or more of these can be used.

  In the present invention, when it is necessary to adjust the molecular weight of the polymer during emulsion polymerization, a compound having a chain transfer ability can be used as the molecular weight modifier, and examples of such compounds include lauryl mercaptan, octyl mercaptan, Examples include mercaptans such as dodecyl mercaptan, 2-mercaptoethanol, octyl thioglycolate, 3-mercaptopropionic acid, and thioglycerin, or α-methylstyrene dimer, and one or a mixture of two or more thereof is used. it can.

Furthermore, since the synthesized aqueous resin dispersion for paper processing may cause problems such as paper burn when processed into paper when acidic, it is preferably neutralized with a neutralizing agent.
Examples of the basic substance used as the neutralizing agent include alkali metal compounds such as sodium hydroxide and potassium hydroxide; or alkaline earth metal compounds such as calcium hydroxide and calcium carbonate; or ammonia; or monomethylamine and dimethyl Examples include water-soluble organic amines such as amine, trimethylamine, monoethylamine, diethylamine, triethylamine, monopropylamine, dimethylpropylamine, monoethanolamine, diethanolamine, dimethylethanolamine, triethanolamine, ethylenediamine, and diethylenetriamine. One or a mixture of two or more can be used. Among these, when it is desired to particularly improve the water resistance of the resulting coating, it is preferable to use ammonia that scatters at room temperature or by heating.

  Next, the processed base material of the present invention includes 15 to 25 parts by weight of a cyano group-containing ethylenically unsaturated monomer (A), 5 to 40 parts by weight of styrene (B), and an amide at a solid content of 100 parts by weight. Group-containing ethylenically unsaturated monomer (C) 2-8 parts by weight, vinyl group-containing silane coupling agent (D) 0.1-1 part by weight, and other ethylenically unsaturated monomers (E ) 26 to 77.9 parts by weight and processed and processed using the aqueous resin dispersion for building material decorative paper processing, which is formed by emulsion polymerization in an aqueous medium.

  The substrate as used in the present invention refers to non-woven fabric (pulp, polyester, etc.), fiber substrate, wood, film, etc. in addition to paper.

  Although it does not specifically limit as a processing method of the process base material of this invention, For example, methods, such as an impregnation process (dipping and spray), coating (an air knife, a roll coater, a flow coater, etc.), a size press process, are mentioned. .

  The characteristics of the processed substrate of the present invention are excellent in inter-paper strength (correlation peeling), ink inking property, solvent resistance, weather resistance, etc., and used in a wide range of applications such as decorative paper for building materials, wallpaper, and building interior materials. Is possible.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention more concretely, this invention is not limited only to these Examples. In the text, “part” and “%” are based on weight unless otherwise specified.
Various physical properties were evaluated by the methods described below.

[Method for evaluating printability]
The resin-impregnated paper for paper processing was solid printed using a gravure printer (HOEI SEIKO CO., LTD, DICOM PROFER DP-II). The density after printing was evaluated according to the following criteria by a colorimeter and visual observation.
Evaluation criteria for printability ○: High density and good characteristics.
Δ: Concentration is low and there is a problem in practical use.
X: The degree of thinness of the density is severe and the characteristics are poor.

[Evaluation method of ink breakthrough]
The ink solvent was dropped on the resin-impregnated paper for paper processing, and the ink back-through state was evaluated according to the following criteria.
Evaluation criteria for ink breakthrough ○: The ink does not penetrate the back of the impregnated paper at all.
Δ: Ink penetrates slightly, but there is no practical problem. X: Ink penetrates and there is a practical problem.

[Evaluation method of inter-paper strength]
Cellophane tape [Trademark: Product No. CT405A, manufactured by NICHIBAN Co., Ltd.] is completely attached to both sides of a resin-impregnated paper for paper processing (15 × 100 mm), and the cellophane tape is peeled off using a peel tester (manufactured by ORIEITEC, TENSIRON). The test was conducted and evaluated by integral average load (gf).
Evaluation standard of inter-paper strength Integral average load (gf)
300 gf or more; Evaluation 5
280 or more and less than 300 gf; Evaluation 4
260 or more and less than 280 gf; Evaluation 3
240 or more and less than 260 gf; Evaluation 2
Less than 240 gf; Evaluation 1

[Evaluation method of heat-resistant roll blocking property]
The resin-impregnated paper for paper processing was cut into 15 × 3 cm, and four samples were placed vertically on a 7 × 15 cm chrome-plated plate and placed on a hot plate set at a surface temperature of 200 ° C. In addition, the sample was used by applying moisture by spraying as necessary.
After being placed on the hot plate, it was loaded with a 1 kg weight, and after 10 minutes, the impregnated paper and the chrome plated plate were peeled off, and the heat resistant roll blocking property was visually evaluated.
○: No blocking and peeling.
X: Blocking occurs and the impregnated paper breaks.

[Example 1]
As shown in Table 1, 81 parts of water was charged into a polymerization vessel equipped with a stirrer, and the temperature was raised to 80 ° C. In a separate container, 10 parts of S-20F [sodium alkylbenzene sulfonate, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.], 50 parts of butyl acrylate, 18.5 parts of methyl methacrylate, 10 parts of styrene, 15 parts of acrylonitrile, 4 parts of acrylamide Then, 2 parts of methacrylic acid, 0.5 part of γ-methacryloxypropyltrimethoxysilane and 30 parts of water were charged, stirred and emulsified to prepare an emulsion.
3% by weight of the emulsion was charged into the polymerization vessel, and 0.5 parts of a 10% aqueous sodium persulfate solution was added to initiate polymerization. The remaining emulsion of the monomer mixture and 5 parts of a 10% aqueous sodium persulfate solution were added dropwise over 4 hours for polymerization. After completion of the dropping, 1 part of a 10% aqueous sodium persulfate solution was added and maintained at 80 ° C. for 2 hours. Next, the mixture was cooled, and the pH of the emulsion was adjusted to 7.0 with aqueous ammonia to obtain an aqueous resin dispersion (1) for processing building paper of the present invention having a viscosity of 345 mPa · s and a solid content of 44.5%.
Water is added to the thus obtained aqueous resin dispersion (1) for processing decorative paper for building materials of the present invention to prepare an impregnating solution having a solid content concentration of 20%. Were dried for 5 minutes and subjected to calendering (70 ° C., linear pressure 70 kg / cm, 2 nip), and various physical properties of the impregnated paper were measured and evaluated. Table 2 shows the measurement results of the impregnated processed paper (1) which is the processed substrate of the present invention.

[Example 2]
As shown in Table 1, 81 parts of water was charged into a polymerization vessel equipped with a stirrer, and the temperature was raised to 80 ° C. In a separate container, 10 parts of S-20F [sodium alkylbenzenesulfonate, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.], 50 parts of butyl acrylate, 19.5 parts of methyl methacrylate, 10 parts of styrene, 15 parts of acrylonitrile, 3 parts of acrylamide Then, 2 parts of acrylic acid, 0.5 part of γ-methacryloxypropyltrimethoxysilane and 30 parts of water were charged, stirred and emulsified to prepare an emulsion.
3% by weight of the emulsion was charged into the polymerization vessel, and 0.5 parts of a 10% aqueous sodium persulfate solution was added to initiate polymerization. The remaining emulsion of the monomer mixture and 5 parts of a 10% aqueous sodium persulfate solution were added dropwise over 4 hours for polymerization. After completion of the dropping, 1 part of a 10% aqueous sodium persulfate solution was added and maintained at 80 ° C. for 2 hours. Next, the mixture was cooled, and the pH of the emulsion was adjusted to 6.8 with aqueous ammonia to obtain an aqueous resin dispersion (2) for processing building paper for the present invention having a viscosity of 455 mPa · s and a solid content of 44.7%.
Using the thus obtained aqueous resin dispersion (2) for processing decorative paper for building materials of the present invention, an impregnated processed paper (2), which is a processed substrate of the present invention, was prepared and measured in the same manner as in Example 1. The results are shown in Table 2.

[Comparative Example 1]
As shown in Table 1, 81 parts of water was charged into a polymerization vessel equipped with a stirrer, and the temperature was raised to 80 ° C. In a separate container, 10 parts of S-20F [sodium alkylbenzenesulfonate, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.], 51 parts of butyl acrylate, 18 parts of methyl methacrylate, 10 parts of styrene, 15 parts of acrylonitrile, 4 parts of acrylamide, methacryl 2 parts of acid and 30 parts of water were charged, stirred and emulsified to prepare an emulsion.
3% by weight of the emulsion was charged into the polymerization vessel, and 0.5 parts of a 10% aqueous sodium persulfate solution was added to initiate polymerization. The remaining emulsion of the monomer mixture and 5 parts of a 10% aqueous sodium persulfate solution were added dropwise over 4 hours for polymerization. After completion of the dropping, 1 part of a 10% aqueous sodium persulfate solution was added and maintained at 80 ° C. for 2 hours. Next, cooling was performed, and the pH of the emulsion was adjusted to 7.0 with aqueous ammonia to obtain an aqueous resin dispersion (3) for veneering decorative paper processing having a viscosity of 364 mPa · s and a solid content of 44.6%.
Using the aqueous resin dispersion (3) for processing decorative paper obtained in this way, an impregnated processed paper (3) as a processed substrate was prepared in the same manner as in Example 1, and the measurement results are shown in Table 2. .

[Comparative Example 2]
As shown in Table 1, 81 parts of water was charged into a polymerization vessel equipped with a stirrer, and the temperature was raised to 80 ° C. In a separate container, 10 parts of S-20F [sodium alkylbenzene sulfonate, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.], 50 parts of butyl acrylate, 15.5 parts of methyl methacrylate, 15 parts of styrene, 15 parts of acrylonitrile, 2 parts of acrylamide Then, 2 parts of acrylic acid, 0.5 part of glycidyl methacrylate and 30 parts of water were charged, stirred and emulsified to prepare an emulsion.
3% by weight of the emulsion was charged into the polymerization vessel, and 0.5 parts of a 10% aqueous sodium persulfate solution was added to initiate polymerization. The remaining emulsion of the monomer mixture and 5 parts of a 10% aqueous sodium persulfate solution were added dropwise over 4 hours for polymerization. After completion of the dropping, 1 part of a 10% aqueous sodium persulfate solution was added and maintained at 80 ° C. for 2 hours. Next, cooling was performed, and the pH of the emulsion was adjusted to 7.0 with aqueous ammonia to obtain an aqueous resin dispersion (4) for processing decorative paper for building materials having a viscosity of 312 mPa · s and a solid content of 44.4%.
Using the aqueous resin dispersion (4) for processing decorative paper obtained in this way, an impregnated processed paper (4) as a processed substrate was prepared in the same manner as in Example 1, and the measurement results are shown in Table 2. .

[Comparative Example 3]
As shown in Table 1, 81 parts of water was charged into a polymerization vessel equipped with a stirrer, and the temperature was raised to 80 ° C. In a separate container, 10 parts of S-20F [sodium alkylbenzenesulfonate, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.], 50 parts of butyl acrylate, 16.5 parts of methyl methacrylate, 10 parts of styrene, 15 parts of acrylonitrile, 6 parts of acrylamide Then, 2 parts of methacryl, 0.5 part of diallyl terephthalic acid ester and 30 parts of water were charged, stirred and emulsified to prepare an emulsion.
3% by weight of the emulsion was charged into the polymerization vessel, and 0.5 parts of a 10% aqueous sodium persulfate solution was added to initiate polymerization. The remaining emulsion of the monomer mixture and 5 parts of a 10% aqueous sodium persulfate solution were added dropwise over 4 hours for polymerization. After completion of the dropping, 1 part of a 10% aqueous sodium persulfate solution was added and maintained at 80 ° C. for 2 hours. Next, the mixture was cooled and the pH of the emulsion was adjusted to 7.0 with aqueous ammonia to obtain an aqueous resin dispersion (5) for processing decorative paper for building materials having a viscosity of 536 mPa · s and a solid content of 44.5%.
Using the aqueous resin dispersion (5) for processing decorative decorative paper thus obtained, impregnated processed paper (5) as a processed substrate was prepared in the same manner as in Example 1, and the measurement results are shown in Table 2. .

[Comparative Example 4]
As shown in Table 1, 79 parts of water was charged into a polymerization vessel equipped with a stirrer and heated to 80 ° C. In a separate container, 10 parts of S-20F [sodium alkylbenzenesulfonate, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.], 51 parts of butyl acrylate, 47 parts of methyl methacrylate, 2 parts of methacrylic acid, and 30 parts of water are charged and stirred. Then, emulsification was performed to prepare an emulsion.
3% by weight of the emulsion was charged into the polymerization vessel, and 0.5 parts of a 10% aqueous sodium persulfate solution was added to initiate polymerization. The remaining emulsion of the monomer mixture and 5 parts of a 10% aqueous sodium persulfate solution were added dropwise over 4 hours for polymerization. After completion of the dropping, 1 part of a 10% aqueous sodium persulfate solution was added and maintained at 80 ° C. for 2 hours. Next, cooling was performed, and the pH of the emulsion was adjusted to 7.0 with aqueous ammonia to obtain a water-based resin dispersion (6) for processing decorative paper for building materials having a viscosity of 14 mPa · s and a solid content of 45.0%.
Using the aqueous resin dispersion (6) for processing decorative paper obtained in this way, an impregnated processed paper (6) as a processed substrate was prepared in the same manner as in Example 1, and the measurement results are shown in Table 2. .

[Comparative Example 5]
As shown in Table 1, 79 parts of water was charged into a polymerization vessel equipped with a stirrer and heated to 80 ° C. In a separate container, 10 parts of S-20F [sodium alkylbenzenesulfonate, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.], 51 parts of butyl acrylate, 37 parts of methyl methacrylate, 10 parts of styrene, 2 parts of methacrylic acid, and 30 parts of water. The mixture was charged, stirred and emulsified to prepare an emulsion.
3% by weight of the emulsion was charged into the polymerization vessel, and 0.5 parts of a 10% aqueous sodium persulfate solution was added to initiate polymerization. The remaining emulsion of the monomer mixture and 5 parts of a 10% aqueous sodium persulfate solution were added dropwise over 4 hours for polymerization. After completion of the dropping, 1 part of a 10% aqueous sodium persulfate solution was added and maintained at 80 ° C. for 2 hours. Next, cooling was performed, and the pH of the emulsion was adjusted to 7.0 with aqueous ammonia to obtain an aqueous resin dispersion (7) for processing decorative paper for building materials having a viscosity of 21 mPa · s and a solid content of 44.9%.
Using the aqueous resin dispersion for processing decorative paper for building materials (7) thus obtained, impregnated processed paper (7) as a processed substrate was prepared in the same manner as in Example 1, and the measurement results are shown in Table 2. .

[Comparative Example 6]
As shown in Table 1, 79 parts of water was charged into a polymerization vessel equipped with a stirrer and heated to 80 ° C. In a separate container, 10 parts of S-20F [sodium alkylbenzene sulfonate, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.], 51 parts of butyl acrylate, 22 parts of methyl methacrylate, 10 parts of styrene, 15 parts of acrylonitrile, 2 parts of methacrylic acid, 30 parts of water was charged, stirred and emulsified to prepare an emulsion.
3% by weight of the emulsion was charged into the polymerization vessel, and 0.5 parts of a 10% aqueous sodium persulfate solution was added to initiate polymerization. The remaining emulsion of the monomer mixture and 5 parts of a 10% aqueous sodium persulfate solution were added dropwise over 4 hours for polymerization. After completion of the dropping, 1 part of a 10% aqueous sodium persulfate solution was added and maintained at 80 ° C. for 2 hours. Next, cooling was performed, and the pH of the emulsion was adjusted to 7.0 with aqueous ammonia to obtain an aqueous resin dispersion (8) for processing decorative paper for building materials having a viscosity of 25 mPa · s and a solid content of 44.6%.
Using the aqueous resin dispersion (8) for building material decorative paper processing thus obtained, an impregnated processed paper (8) as a processed substrate was prepared in the same manner as in Example 1, and the measurement results are shown in Table 2. .

Abbreviations in Table 1 represent the following compound names.
AN; acrylonitrile St; styrene AM; acrylamide MPS; γ-methacryloxypropyltrimethoxysilane BA; butyl acrylate MMA; methyl methacrylate AA; acrylic acid MAA; methacrylic acid GMA; glycidyl methacrylate DAP;

The aqueous resin dispersion for processing decorative paper of the present invention has excellent film-forming properties and solvent resistance, and is mechanically stable and chemically stable when used as a paper processing agent, particularly as a binder resin for decorative paper for building materials. In addition to excellent heat resistance and storage stability, heat-resistant roll blocking properties and excellent paper-to-paper strength of the processed paper, the processed substrate using the aqueous resin dispersion for processing decorative paper of the present invention has inter-paper strength and printability. It is extremely useful as a processing substrate because it has excellent processability, blocking due to ink back-through, and heat roll blocking during calendering, and it is extremely useful as a processing substrate. In addition to paper such as decorative decorative paper, non-woven fabric (pulp, polyester, etc.) It can be used in a wide variety of fields such as fiber base materials, wood, and films.

Claims (3)

When the aqueous resin dispersion has a solid content of 100 parts by weight, the cyano group-containing ethylenically unsaturated monomer (A) 15 to 25 parts by weight, the styrene (B) 5 to 40 parts by weight, the amide group-containing ethylenically unsaturated monomer 2-8 parts by weight of a saturated monomer (C), 0.1-1 part by weight of a vinyl group-containing silane coupling agent (D), and 26-77. An aqueous resin dispersion for processing decorative paper for building materials, comprising 9 parts by weight and emulsion-polymerized in an aqueous medium. The aqueous resin dispersion for building material decorative paper processing according to claim 1, wherein the amide group-containing ethylenically unsaturated monomer (C) is (meth) acrylamide. In 100 parts by weight of solid content, 15 to 25 parts by weight of cyano group-containing ethylenically unsaturated monomer (A), 5 to 40 parts by weight of styrene (B), and amide group-containing ethylenically unsaturated monomer (C 2-8 parts by weight, vinyl group-containing silane coupling agent (D) 0.1-1 part by weight, and other ethylenically unsaturated monomer (E) 26-77.9 parts by weight A processed substrate obtained by using an aqueous resin dispersion for processing decorative paper for building materials, which is obtained by emulsion polymerization in an aqueous medium.