JP3484682B2 - Resin composition for paper coating - Google Patents

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 paper coating, which is excellent in solvent resistance, blocking resistance and gloss when coated on paper.

It can be used for applications in which the coated surface is required to have solvent resistance and blocking resistance, such as anti-curl agents for paper and undercoat agents for release paper.

[0003]

2. Description of the Related Art An undercoating agent for release paper is used as an application requiring solvent resistance, blocking resistance and gloss impartment.

Conventionally, a silicone release agent diluted with a solvent such as toluene, xylene or hexane has been used as a release agent component used in release paper. This silicone release agent is expensive, and it is necessary to obtain a sufficient release property with a coating amount as small as possible.

Therefore, in general, the undercoating agent layer is subjected to sealing treatment so that the silicone release agent does not penetrate into the paper, and then the silicone release agent is applied. Therefore,
The undercoat agent is required to have solvent barrier properties and solvent resistance to the above-mentioned solvent.

In addition to the above items, the undercoating agent is required to have blocking resistance during storage of the coated material and high gloss for imparting a high-grade feeling to the release paper. Regarding an undercoat agent for release paper having excellent solvent resistance, JP-A-4-209682 discloses a copolymer obtained by emulsion polymerization of an acrylic acid ester having a hydroxyl group and another ethylenically unsaturated monomer. Methods using polymer emulsions are described.

However, even when the emulsion described in the above publication is used as an undercoating agent, it cannot be said that the solvent barrier property and gloss are still sufficiently satisfactory. In the above publication, in order to improve the solvent resistance, the hydroxyl group-containing acrylates are emulsion-polymerized, but the copolymerization amount of the monomer is increased (for example, about 30% by weight in all the polymerizable monomers). )
Then, the emulsion stability and the storage stability of the obtained emulsion decrease, which is not preferable.

The decrease in emulsion stability can be prevented by using a relatively large amount of a surfactant, but the increase in free low molecular weight components resulting from the surfactant significantly reduces the solvent resistance, resulting in a solvent barrier. The sex becomes worse.

Further, when a large amount of a surfactant is used, the moisture resistance also deteriorates, and there is a drawback that blocking is likely to occur when stored only with the undercoat layer when the humidity is high.
As another method for supplementing the solvent resistance, there is a method in which a crosslinkable monomer is copolymerized to crosslink the copolymer molecule to make it three-dimensional.

However, when used for paper coating,
Cross-linking to the extent that solvent resistance is improved has a drawback of impeding repulping when recycling paper.

[0011]

DISCLOSURE OF THE INVENTION The present invention provides a resin composition for paper coating which overcomes the above-mentioned drawbacks of the prior art and imparts excellent solvent barrier properties, blocking resistance and gloss to the resin coated surface. It is a thing.

[0012]

Means for Solving the Problems The inventors of the present invention have made extensive studies on a water-dispersible resin that exhibits excellent solvent barrier properties and solvent resistance, and forms a film having good blocking resistance and gloss. A stable emulsion is obtained by emulsion-polymerizing a hydroxyl group-containing ethylenically unsaturated monomer (B) using a sulfonic acid group-containing polymer dispersant in place of the emulsion dispersant used in ordinary emulsion polymerization, It was found that a film having excellent solvent resistance and blocking resistance was formed, and the invention was completed.

It was also found that the polymer aqueous dispersion obtained by the present invention has good film-forming properties and can impart gloss with excellent coatability. That is, the present invention is a water-soluble polymer (A) obtained by polymerizing a sulfonic acid group- and / or sulfate group-containing ethylenically unsaturated monomer (a) as an essential component.
In the presence of the above, an emulsion polymerization of a hydroxyl group-containing ethylenically unsaturated monomer (B) and an ethylenically unsaturated monomer (C) copolymerizable with the monomer (B) in an aqueous medium is carried out. It is intended to provide a resin composition for paper coating, which contains coalesced particles and is excellent in solvent barrier properties, solvent resistance, blocking resistance, and gloss.

The hydroxyl group-containing ethylenically unsaturated monomer (B) used as an essential component of the copolymer in the present invention has the monomer species itself described in JP-A-4-209682.
However, in the present invention,
It is not only necessary to use the essential component (B), but a sulfonic acid group-containing polymer dispersant may be used as an emulsifying dispersant used in emulsion polymerization.
By polymerizing the above, a synergistic effect which cannot be imagined from the effect disclosed in the above publication is obtained.

The water-soluble polymer (A) used as the emulsifying dispersant in the present invention is an ethylene which is capable of copolymerizing the sulfonic acid group- and / or sulfate group-containing ethylenically unsaturated monomer (a) alone or with it. It is a compound obtained by polymerizing a polyunsaturated monomer (b).

The sulfonic acid group- and / or sulfate group-containing ethylenically unsaturated monomer (a) includes a sulfonic acid group and / or sulfate group (and / or salt thereof) and a polymerizable unsaturated group in the molecule. It is not particularly limited as long as it has and, for example, vinyl group-containing sulfonic acids such as vinyl sulfonic acid, styrene sulfonic acid or salts thereof, allyl sulfonic acid, allyl group-containing sulfonic acids such as 2-methylallyl sulfonic acid or Salts thereof, (meth) acrylate-containing sulfonic acids such as 2-sulfoethyl (meth) acrylate, 2-sulfopropyl (meth) acrylate or salts thereof, (meth) such as (meth) acrylamide-t-butyl sulfonic acid Acrylic group-containing sulfonic acids or salts thereof, or radical slurries commonly referred to as reactive emulsifiers Emulsifier containing a polymerizable unsaturated group, it can also be used those having a sulfonic acid group as the hydrophilic group, one or more mixtures thereof can be used.

The polymerizable monomer component for synthesizing the water-soluble polymer (A) may be composed only of the sulfonic acid group- and / or sulfate group-containing ethylenically unsaturated monomer (a). If necessary, other polymerizable monomer may be used in combination as the copolymerization component (b).

Examples of the copolymerization component (b) include unsaturated acids such as (meth) acrylic acid and itaconic acid, methyl (meth) acrylate, ethyl (meth) acrylate,
n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth)
Acrylic esters such as acrylate, glycidyl (meth) acrylate, dimethylaminolethyl (meth) acrylate, vinyl esters such as vinyl acetate, (meth) acrylamide, N-methylol (meth) acrylamide, N-butoxymethyl (meth ) Acrylamide,
Unsaturated acid amides such as diacetone acrylamide or derivatives thereof, nitriles of unsaturated carboxylic acids such as (meth) acrylonitrile, aromatic vinyl compounds such as styrene and α-methylstyrene, N-vinylpyrrolidone and the like, These 1 type, or 2 or more types of mixture can be used.

In particular, when a carboxyl group-containing ethylenically unsaturated monomer is used as the copolymerization component (b), the stability of the emulsion during emulsion polymerization becomes better, and
The solvent resistance of the obtained film can be improved at the same time.

The carboxyl group-containing ethylenically unsaturated monomer used as the copolymerization component (b) is not particularly limited as long as it has a carboxyl group and / or its salt and a polymerizable unsaturated group in the molecule. Not, for example (meta)
Examples thereof include acrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, half-esters thereof or salts thereof, and one kind or a mixture of two or more kinds thereof can be used.

Further, in synthesizing the water-soluble polymer (A), a compound having a chain transfer ability as a molecular weight modifier,
For example, mercaptans and the like may be added. The method for producing the water-soluble polymer (A) may be either bulk polymerization or solution polymerization depending on its properties, but a method using a medium in which the raw material and the product are uniformly dissolved is preferable.

As such a medium, any one can be used as long as it dissolves the polymerizable monomer and the radical polymerization initiator to be used and does not inhibit the radical polymerization. For example, when water is used as the medium, the obtained water-soluble The polymer (A) does not need to be subjected to solvent removal treatment and can be used as it is for emulsion polymerization, and the manufacturing process can be simplified.

The hydroxyl group-containing ethylenically unsaturated monomer (B) used in the production of the aqueous polymer dispersion of the present invention is
It has a hydroxyl group and a polymerizable unsaturated group in the molecule, and for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3
-Hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, glycerol mono (meth) acrylate and the like can be mentioned, and one kind or a mixture of two or more kinds thereof can be used.

Hydroxyl group-containing ethylenically unsaturated monomer (B)
Significantly improves the solvent barrier property, solvent resistance, blocking resistance, and film-forming property, and the amount used is such that the hydroxyl group-containing ethylenically unsaturated monomer (B) can be copolymerized with the monomer. 10 to 60 parts by weight is preferable with respect to 100 parts by weight in total with the ethylenically unsaturated monomer (C).

When the amount of the polymerizable monomer (B) used is less than 10 parts by weight, it becomes difficult to obtain the above-mentioned improving effects. On the other hand, if it is used in excess of 60 parts by weight, the polymerization stability during emulsion polymerization may deteriorate and a large amount of aggregates may be generated, or the emulsion may solidify (gel) during polymerization or storage. , A stable emulsion cannot be obtained.

Examples of the other ethylenically unsaturated monomer (C) copolymerizable with the above monomer (B) include unsaturated acids such as (meth) acrylic acid and itaconic acid, and methyl (meth).
Acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth)
Acrylic esters such as acrylate, glycidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, vinyl esters such as vinyl acetate, (meth) acrylamide, N-methylol (meth) acrylamide, N-butoxymethyl (meth) Acrylamide,
Unsaturated acid amides such as diacetone acrylamide or derivatives thereof, nitriles of unsaturated carboxylic acids such as (meth) acrylonitrile, aromatic vinyl compounds such as styrene and α-methylstyrene, N-vinylpyrrolidone and the like, These 1 type, or 2 or more types of mixture can be used.

In particular, when a carboxyl group-containing ethylenically unsaturated monomer is used as the copolymerization component (C), the stability of the obtained emulsion can be improved and the solvent resistance can be further improved.

The carboxyl group-containing ethylenically unsaturated monomer used as the copolymerization component (C) is not particularly limited as long as it has a carboxyl group and / or its salt and a polymerizable unsaturated group in the molecule. Not, for example (meta)
Examples thereof include acrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, half-esters thereof or salts thereof, and one kind or a mixture of two or more kinds thereof can be used.

When the water-dispersible resin of the present invention is used for paper coating, especially for applications requiring paper recycling, if the resin is crosslinked and becomes three-dimensional, repulping is hindered. Not preferable.

Therefore, use of a monomer having a crosslinkable functional group or a polyfunctional monomer having two or more vinyl groups as the monomer (C) causes deterioration of repulping. Therefore, it is necessary to minimize the amount used.

However, in order to further improve the solvent resistance, a method of cross-linking the resin to make it three-dimensional is an effective means. In the present invention, a carboxyl group-containing monomer is used as the above-mentioned monomer (C), polyvalent metal salts are added to the obtained water-dispersible resin, and reversible ionic crosslinking is carried out between the carboxyl group and the polyvalent metal. It was found that the solvent resistance can be improved by inhibiting the repulping by applying the above.

Examples of the polyvalent metal salts to be added include metal ions such as zinc, aluminum, calcium, cobalt, zirconium, chromium and magnesium, and these salts, for example, nitrates, sulfates, hydrochlorides, acetates, carbonates. Examples thereof include water-soluble polyvalent metal salts such as salts, naphthenates, fatty acid salts, and ammonium salts, and one or a mixture of two or more thereof can be used.

The polyvalent metal salt is preferably added in an amount of 0.1 to 2 equivalents with respect to the copolymerized carboxyl groups. Regarding the polymerization method when emulsion-polymerizing the monomers (B) and (C) using the above water-soluble polymer (A) as an emulsion dispersant, any conventionally known emulsion polymerization method, for example, a monomer dropping method, It can be synthesized by a pre-emulsion method, a seed polymerization method, a multi-stage polymerization method, or the like.

The amount of the water-soluble polymer (A) used as the emulsifying dispersant is not particularly limited, but the hydroxyl group-containing ethylenically unsaturated monomer (B) used for emulsion polymerization and the monomer can be copolymerized. Total 10 with other ethylenically unsaturated monomers (C)
Used in an amount of about 0.5 to 30 parts by weight with respect to 0 parts by weight,
In order to maintain polymerization stability and emulsion stability during storage, it is preferably used in the range of 1 to 30% by weight.

It is also possible to add a hydrophilic solvent and other known emulsifiers and additives at the time of emulsion polymerization, but the amount used should be kept within a range that does not adversely affect the physical properties of the film. There is.

The solid content concentration during polymerization is usually 20 to
About 70% by weight, preferably about 30-60% by weight is suitable. Further, as the polymerization initiator used in the polymerization, a radical polymerization initiator is used, for example, potassium persulfate, persulfates such as ammonium persulfate, benzoyl peroxide, organic peroxides such as cumene hydroxyl peroxide, There are hydrogen peroxide and the like, radical polymerization using only these peroxides, or can be polymerized by redox polymerization using a combination of the peroxide and a reducing agent such as sodium acid sulfite, sodium thiosulfate, Further, 4,4'-azobis (4-cyanopentanoic acid), 2,2'-azobis (2-amidinopropane)
It is also possible to use an azo initiator such as a dihydrochloride.

If necessary, a chain transfer agent such as mercaptans can be added. The polymerization temperature varies depending on the type of the monomer used, the type of the polymerization initiator, etc., but usually a temperature range of 30 to 80 ° C. is suitable.

The particle size of the aqueous emulsion of the present invention is 3
0 to 1000 nm is suitable, but 700 nm or less is preferable from the viewpoint of film forming property of the film. The paper coating resin composition containing the polymer aqueous dispersion of the present invention thus obtained can be used alone as the polymerizable aqueous dispersion, but within a range that does not impair the desired effects of the present invention. , Water-soluble polymers such as celluloses, starch, polyvinyl alcohol, fillers,
Thickener, pH adjuster, water repellent, leveling agent, defoaming agent,
A film forming auxiliary agent and the like can be added as appropriate.

The resin composition for paper coating of the present invention can be used for applications in which anti-curl agent for paper, undercoat agent for release paper, solvent resistance and blocking resistance are required on the coated surface. .

In particular, when it is used as an undercoat agent in the production of release paper, it works well as a sealing agent for the release agent coating liquid when a solvent-type release agent is applied thereon, Further, it is excellent in blocking resistance when stored only with the undercoat layer, and good gloss can be imparted to the obtained release paper.

[0041]

EXAMPLES The present invention will now be specifically described with reference to examples, but the scope of the present invention is not limited to these examples. Hereinafter, unless otherwise specified,% means% by weight and part means part by weight.

Reference Example 1 A flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube and a thermometer was charged with 500 parts of deionized water, and the internal temperature was raised to 80 ° C. while blowing nitrogen.

Then, sodium styrenesulfonate 15
Charge 0 parts and ammonium persulfate 14.3 parts, 80 ℃
Polymerization was carried out for 3 hours to obtain an aqueous solution of a polymer having a solid content of 30.5%. This is referred to as polymer (A) -1.

Reference Example 2 The same flask as in Reference Example 1 was charged with 500 parts of deionized water, and the internal temperature was raised to 80 ° C. while blowing nitrogen.

Then, sodium styrenesulfonate 75
Parts, 75 parts of acrylic acid and 14.3 parts of ammonium persulfate were charged and polymerized at 80 ° C. for 3 hours to obtain an aqueous solution of a polymer having a solid content of 30.5%.

This is designated as Polymer (A) -2. Example 1 148 parts of deionized water in a flask equipped with a dropping funnel, a stirrer, a reflux condenser, a nitrogen inlet tube, and a thermometer, and the polymer (A) -1 (aqueous solution) obtained in Reference Example 1 as an emulsifying dispersant. 1
0 part was charged and the internal temperature was raised to 80 ° C. while blowing nitrogen.

Subsequently, 1 part of ammonium persulfate was added, and then a mixture of 15 parts of n-butyl acrylate, 30 parts of ethyl acrylate, 45 parts of methyl methacrylate and 10 parts of 2-hydroxyl ethyl methacrylate was continuously added for 2 hours. Dropped into the flask.

During the dropping, the temperature was maintained at 75 to 80 ° C., and after the dropping was completed, the mixture was stirred at the same temperature for 1 hour to terminate the polymerization. After that, the pH was adjusted to 7 with aqueous ammonia and the solid content was 4
0% polymer aqueous dispersion 1 was obtained.

Examples 2 to 6 The same as Example 1 except that the amount and type of the polymer (A) (aqueous solution) and the composition of the polymerizable monomer mixture are as shown in Table 1. The above procedure was repeated to obtain polymer aqueous dispersions 2 to 6.

The results are summarized in Table 1. Example 7 To 100 parts of the polymer aqueous dispersion obtained in Example 5,
7 parts of a 10% aqueous solution of zinc acetate dihydrate was added.

The results are summarized in Table 1. Comparative Examples 1-2 In Example 1, emulsion polymerization was carried out using sodium polyoxyethylene alkylphenyl ether sulfate as an emulsifier instead of the polymer (A).

The same procedures as in Example 1 were repeated except that the amount of the emulsifier and the composition of the polymerizable monomer mixture were as shown in Table 1 to obtain aqueous dispersions 1'-2 'of comparative polymers. It was The results are summarized in Table 1.

[0053]

[Table 1]

* 1 The amount of polymer (A) -1 and polymer (A) -2 used is expressed in parts by weight of solid content. * 2 Emulsifier = sodium polyoxyethylene alkylphenyl ether sulfate is the weight of solid content. Displayed in parts * 3 Polymerization stability ◯: Good polymerization stability Δ: Small amount of aggregates generated during polymerization ×: Large amount of aggregates generated during polymerization * 4 Zinc acetate is a 10% aqueous solution of zinc acetate dihydrate. Addition of 7 parts to 100 parts of combined aqueous dispersion * 5 Minimum film forming temperature BA: n-butyl acrylate EA: ethyl acrylate MMA: methyl methacrylate AN: acrylonitrile HEMA: 2-hydroxyethyl methacrylate HPA: 2-hydroxypropyl acrylate AA : Acrylic acid

[0055]

【Evaluation methods】

"Solvent resistance" (1) Solvent immersion test of film The aqueous polymer dispersions obtained from Examples 1 to 7 and Comparative Examples 1'and 2'are coated on a glass plate and kept at room temperature for 3 days. The film was left to stand and a 0.5 mm thick film was prepared.

The film was dried at 140 ° C. for 5 minutes,
The residual water was removed. The obtained film is 50 mm
Exactly cut into corners (S ₀ ) to obtain test pieces. Next, this test piece was immersed in a toluene solution at room temperature, the area (S ₁ ) of the test piece was measured at a predetermined time, and the area swelling ratio of the film with toluene was determined according to the following formula.

[0057] (2) Solvent rubbing test of paper coatings Polymer aqueous dispersions 1 to 1 obtained from Examples and Comparative Examples
7, 2'was coated on a commercially available high-quality paper (grammage 70 g / cm ² ) with a bar coater # 20 and dried at 120 ° C for 1 minute to prepare a test paper.

The resin coated surface of the obtained test paper was rubbed 50 times with a cotton swab impregnated with a toluene solution, and the deterioration of the coated surface was observed. ○: No abnormality at all △: Slight deterioration on the surface ×: Significant deterioration to the inside (3) Solvent barrier test of paper coating Create a test paper in the same manner as the solvent rubbing test, and apply a toluene solution to the test paper. Then, the normal state of permeation of toluene was observed.

○: No soaking △: Partially soaking ×: Many soaking "blocking resistance" Blocking test of paper coating A test paper was prepared in the same manner as the solvent rubbing test, and the resin coated surfaces were put together, A calender roll was passed at a linear pressure of 30 Kg / cm, and the degree of blocking was observed.

○: No blocking Δ: Partially blocking ×: Blocking on the entire surface “Gloss” Gloss of paper coating A test paper was prepared in the same manner as the solvent rubbing test, and the specular gloss at 60 ° was measured. did.

Table 2 shows the results of the solvent resistance test, solvent rubbing test, solvent barrier test, blocking property test, and gloss measurement.

[0062]

[Table 2]

[0063]

The resin composition for paper coating of the present invention comprises a water-soluble polymer (A) containing a sulfonic acid group as an emulsifying dispersant, and a hydroxyl group-containing ethylenically unsaturated monomer (B).
And a polymer particle obtained by emulsion-polymerizing another polymerizable monomer (C), and a film having excellent solvent resistance, blocking resistance, and gloss can be obtained.

By using the water-soluble polymer (A) as the emulsifying dispersant, a stable emulsion can be obtained even if a relatively large amount of the hydroxyl group-containing ethylenically unsaturated monomer (B) is copolymerized. A film having excellent solvent resistance, film forming properties, and good blocking resistance can be obtained.

Further, when a carboxyl group-containing ethylenically unsaturated monomer is introduced as a copolymerization component into the water-soluble polymer (A) and / or polymer particles obtained by emulsion polymerization, the solvent resistance is further improved.

Further, when a polyvalent metal salt is added to this copolymer aqueous dispersion, reversible ionic cross-linking is formed between the introduced carboxyl groups and metal ions, and solvent resistance is further improved.

The resin composition for paper coating of the present invention, when used as an undercoating agent for release paper, has excellent solvent barrier properties, has no blocking when winding the resin coated product, and has a glossy coated surface. Can be given.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP 59-98186 (JP, A) JP 60-192718 (JP, A) JP 4-213377 (JP, A) JP 5- 43830 (JP, A) (58) Fields surveyed (Int.Cl. ⁷ , DB name) C09D 1/00-10/00 C09D 101/00-201/10 D21B 1/00-1/38 D21C 1/00 -11/14 D21D 1/00-5/28 D21F 1/00-13/12 D21G 1/00-9/00 D21H 11/00-27/42 D21J 1/00-7/00

Claims (8)

(57) [Claims] 1. An aqueous solution obtained by polymerizing a sulfonic acid group- and / or sulfate group-containing ethylenically unsaturated monomer (a) alone or with an ethylenically unsaturated monomer (b) copolymerizable therewith. In the presence of the organic polymer (A), the hydroxyl group-containing ethylenically unsaturated monomer (B) and another ethylenically unsaturated monomer (C) copolymerizable with the monomer (B) are mixed with an aqueous solution. A resin composition for paper coating, comprising an aqueous polymer dispersion (D) polymerized in a medium. 2. A hydroxyl group-containing ethylenically unsaturated monomer (B)
Is 10 to 100 parts by weight in total of the hydroxyl group-containing ethylenically unsaturated monomer (B) and the other ethylenically unsaturated monomer (C) copolymerizable with the monomer (B). The resin composition for paper coating according to claim 1, which is 60 parts by weight. 3. The resin composition for paper coating according to claim 1, wherein the ethylenically unsaturated monomer (b) is a carboxyl group-containing ethylenically unsaturated monomer. . 4. The resin composition for paper coating according to claim 1 or 2, wherein the ethylenically unsaturated monomer (C) is a carboxyl group-containing ethylenically unsaturated monomer. . 5. The method according to claim 3, further comprising a polyvalent metal salt.
Alternatively, the resin composition for paper coating according to claim 4. 6. A water-soluble polymer (A) is a hydroxyl group-containing ethylenically unsaturated monomer (B) and another ethylenically unsaturated monomer (C) copolymerizable with the monomer (B). The resin composition for paper coating according to any one of claims 1 to 5, which is 0.5 to 30 parts by weight based on 100 parts by weight in total. 7. The paper coating according to claim 5 or 6 , wherein the polyvalent metal salt is used in an amount of 0.1 to 2 equivalents with respect to the carboxyl groups of the polymer aqueous dispersion (D). Resin composition. 8. An undercoat agent for release paper, comprising the resin composition for paper coating according to claim 1.