JP2864222B2 - Binder composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a binder composition used for producing a coated paper for rotary offset printing and a coated paper for rotary offset printing.

[0002]

2. Description of the Related Art Recently, as a coated paper for rotary offset printing, a coating solution containing a latex having a gel content in a certain range (70 to 95% by weight) is applied by a curtain coating method in a certain range. One having an undercoating layer having air permeability (Japanese Patent Application Laid-Open No. Hei 4-100998) has been proposed. According to this method, a coating layer having high air permeability is obtained by applying the coating layer in a manner that does not compress the coating layer. However, when the gel content exceeds 70% by weight, the blister resistance effect is lost, and The smoothing effect by the processing is lost.

[0003]

The method further comprises:
Since no pressure is applied during coating, the smoothness of the coated surface becomes insufficient, the gloss of white paper and the gloss of printing become insufficient, and it cannot be applied to the top coat of single-coated paper or double-coated paper. There's a problem.

[0004]

The inventor of the present invention has proposed a coating method other than a curtain coating method (such as a blade coater).
As a result of diligent studies on the method of producing coated paper for rotary offset printing excellent in blister resistance, the amount of emulsifier in the aqueous phase is small, with the resin latex having a specific glass transition temperature and a certain temperature as a boundary By using a coating liquid that combines a vinyl polymer whose hydrophilicity and hydrophobicity change reversibly, the coating for rotary offset printing is excellent in air permeability, blister resistance and smoothness even by a normal coating method. The present inventors have found that paper can be obtained, and have reached the present invention.

That is, according to the present invention, the amount of the emulsifier in the aqueous phase is
The resin latex (A) having a glass transition temperature of −20 to 50 ° C. which is 0.01 mmol / g (resin) or less, and a constant temperature selected from the group consisting of the following (B1) to (B5): A binder composition for producing coated paper for rotary offset printing, characterized by containing a vinyl polymer (B) whose hydrophilicity and hydrophobicity change reversibly at the boundary and become gelled by heating; and the composition. This is a coated paper for rotary offset printing, comprising a coated layer formed from a material. (B1): a polymer comprising a vinyl carboxylate (b) of an alkylene oxide adduct of a cyclic amine or an acyclic amine having 5 or more carbon atoms, (B2): an N-alkyl or N-alkylene (meth)
(B3): a polymer comprising polyalkylene glycol monoalkyl ether mono (meth) acrylate or polyalkylene glycol monophenyl ether mono (meth) acrylate; (B4): a polymer comprising polyalkylene glycol monoalkyl monovinyl ether (B5): a polymer comprising polyalkylene glycol monophenyl monovinyl ether.

[0006] The amount of the emulsifier in the aqueous phase in the resin latex (A) in the present invention is 0.01 mmol (mmol).
/ G (resin) or less, preferably 0.002 mmol /
g. The amount of the emulsifier in the aqueous phase is 0.
If it exceeds 01 mmol / g, the effect of the vinyl polymer (B) that “hydrophilicity and hydrophobicity reversibly change at a certain temperature boundary” is inhibited, and as a result, the gloss is high,
It becomes difficult to obtain a binder composition for coated paper that gives coated paper for rotary offset printing with good printability (hereinafter simply referred to as coated paper). The amount of the emulsifier in the aqueous phase is represented by the weight of the resin component in the resin latex (A).

The amount of the emulsifier in the aqueous phase can be determined by analyzing and quantifying the aqueous phase obtained by removing the resin component from the resin latex by liquid chromatography or the like. As a method of removing the resin component from the resin latex, for example, a method of removing the resin component by coagulating and solidifying the resin component after freezing the resin latex, a method of removing the resin component by sedimentation and solidification by a centrifugal separator, an acid or an alkali. In addition, a method of removing and solidifying and removing the resin component may be used.

As a method for producing a resin latex having an emulsifier amount of 0.01 mmol / g or less in an aqueous phase, for example,
A method of emulsion polymerization of a monomer using an emulsifier having low solubility in water, a method of emulsion polymerization using an emulsifier having a radical polymerizable group, a method of emulsion polymerization using a water-soluble polymer as a protective colloid, an organic solvent After synthesizing a polymer obtained by (co) polymerizing an ion-forming monomer therein, neutralizing the obtained polymer with an acid or alkali, adding water, emulsifying the polymer, and removing the solvent.

Among these methods, an emulsion polymerization method is preferable in that a latex composed of a high molecular weight resin is obtained, and an emulsifier having a radical polymerizable group (SBR latex is preferable in that an SBR latex is easily obtained under ordinary conditions). Emulsion polymerization using a) is particularly preferred.

The emulsifier having low solubility in water includes HL
B value of 3 to 9, for example, amine or alkali metal salt of a fatty acid having 22 or more carbon atoms, ethylene oxide 1 to 6 of an aliphatic or aromatic alcohol having 15 or more carbon atoms
And a molar adduct.

An emulsifier (a) having a radical polymerizable group;
For example, (1) anionic (meth) acrylates represented by the following formula
And the like indicated by: CH₂= C (R³) CO₂(CH₂)_mSO₃M CH₂= C (R³) CO₂CH₂C (R⁴) (OCOR)⁵) CH₂SO₃M CH₂= C (R₃) CO₂CH₂CH₂OCOArCO₂CH₂CH₂OSO₃ M CH₂= C (R₃) CO₂(AO)_pSO₃M (where R³Is a hydrogen atom or a methyl group, and m is an integer of 1 to 4.
The number M is an alkali metal ion, ammonium ion or
Is an aminium ion, R⁴Is a hydrogen atom or a methyl group,
R⁵Is an alkyl group or alkenyl having 7 to 21 carbon atoms
Group, Ar is an aromatic or aliphatic ring, AO has 2 to 2 carbon atoms
An oxyalkylene group of 4, p is an integer of 2 to 30
You. (2) Anionic allyl compounds, represented by the following formula
Etc .: CH₂= CHCH₂OCOCH (SO₃M) CH₂CO₂R⁵  CH₂= CHCH₂OCH₂CH (OH) CH₂OCOCH (SO₃M) CH₂ CO₂R⁵(R⁶) (R⁷) Ar (CH₂CH = CH₂) O (AO)_qSO₃  M (where M is an alkali metal ion or an ammonium ion
Or aminium ion, R⁵Is an alk having 7 to 21 carbon atoms
R or alkenyl, R⁶Is an alkyl having 4 to 18 carbon atoms
A kill group, an alkenyl group or an aralkyl group, R⁷Is hydrogen
An atom or an alkyl or alkenyl group having 4 to 18 carbon atoms
Or an aralkyl group, Ar is an aromatic ring, AO is a carbon number
2 to 4 oxyalkylene groups, q is an integer of 2 to 200
Show. (3) Anionic maleic esters represented by the following formula
Things: R⁸OCOCH = CHCO₂CH₂CH (OH) CH₂SO₃M R⁹O (AO)_qCOCH = CHCO₂(CH₂)_rCH (R¹⁰) SO₃M R⁹(AO)_qOCOCH = CHCO₂M (where R⁸Is an alkyl group having 5 to 21 carbon atoms, alkenyl
Group or aralkyl group, M is an alkali metal ion,
Monium ion or aminium ion, R⁹And R
¹⁰Is an alkyl group having 1 to 21 carbon atoms, an alkenyl group or
Represents an aralkyl group, and AO represents an oxyalkylene having 2 to 4 carbon atoms.
And q represents an integer of 2 to 200, and r represents an integer of 0 to 3.
You. (4) Anionic itaconic esters represented by the following formula:
Thing: CH₂= C (CH₂CO₂R⁸) CO₂(CH₂)_mSO₃M CH₂= C (CH₂CO₂R⁸) CO₂CH₂CH (OH) CH₂SO₃M (where R⁸Is an alkyl group having 5 to 21 carbon atoms, alkenyl
M or an aralkyl group, m is an integer of 1-4, M is
Li metal ion, ammonium ion or aminium ion
Indicates ON. (5) Nonionic (meth) acrylates, the following formula
And the like indicated by: CH₂= C (R³) CO (AO)_qOR⁸  CH₂= C (R³) CO (PO)_q(EO)_sOH or CH₂= C (R³) CO (EO)_q(PO)_sOH (where R³Is a hydrogen atom or a methyl group, R⁸Is carbon number 5
To 21 alkyl groups, alkenyl groups or aralkyl
AO is an oxyalkylene group having 2 to 4 carbon atoms, q is 2
An integer of ~ 200, PO is an oxypropylene group, EO is
A xyethylene group, s represents an integer of 2 to 200. (6) Nonionic allyl compounds represented by the following formula
Etc .: (R⁶) (R⁷) Ar (CH₂CH = CH₂) O (AO)_qH (where R⁶Is an alkyl group having 4 to 18 carbon atoms, alkenyl
Or an aralkyl group, R⁷Is a hydrogen atom or carbon number
4 to 18 alkyl groups, alkenyl groups or aralkyl
Group, Ar is an aromatic ring, AO is an oxy group having 2 to 4 carbon atoms.
A alkylene group, and q represents an integer of 2 to 200. (7) Nonionic maleic esters represented by the following formula
Things: R⁶(AO)_qOCOCH = CHCO₂(AO)_sR⁷ (Where R⁶Is an alkyl group having 4 to 18 carbon atoms, alkenyl
Or an aralkyl group, R⁷Is a hydrogen atom or carbon number
4 to 18 alkyl groups, alkenyl groups or aralkyl
AO is an oxyalkylene group having 2 to 4 carbon atoms, q and
And s represents an integer of 2 to 200. (8) Nonionic itaconic esters represented by the following formula:
Thing: CH₂= C [CH₂CO₂(AO)_qR⁶] CO₂(AO)_sR⁷ (Where R⁶Is an alkyl group having 4 to 18 carbon atoms, alkenyl
Or an aralkyl group, R⁷Is a hydrogen atom or carbon number
4 to 18 alkyl groups, alkenyl groups or aralkyl
AO is an oxyalkylene group having 2 to 4 carbon atoms, q and
And s represents an integer of 2 to 200. (9) Cationic (meth) acrylates, the following formula
Etc .: [CH₂= C (R³) COOCH₂CH (OH) CH₂N (R¹¹)₃] X (where R³Is a hydrogen atom or a methyl group, R¹¹Is the carbon number
4 to 21 alkyl groups, alkenyl groups or aralkyl
The group, X, represents a halogen atom. (10) Cationic allyl compounds represented by the following formula
Etc .: [CH₂= CHCH₂CH (OH) CH₂N (CH₃)₂R¹¹] X [CH₂= CHCH₂N (CH₃)₂R¹¹] X (where R¹¹Is an alkyl group having 4 to 21 carbon atoms, alkenyl
And X represents a halogen atom. )

Among them, (1), (5) and (5) are preferred in that they have good copolymerizability with various monomers, especially with styrene.
(9) is preferable, and (1) to (4) are preferable in that they are hardly aggregated by a pigment dispersant [for example, sodium poly (meth) acrylate] used in a normal coating color. Among (1), (meth) acrylates having an anionic group and a polyoxypropylene chain are particularly preferred.

The amount of (a) used when producing the resin latex is usually 0.1 to 20% by weight based on the resin content.

The resin constituting the resin latex (A) in the present invention is a (co) polymer of various monomers. The monomer is not particularly limited. For example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, octadecyl (meth) acrylate, glycidyl (meth) Acrylates, N, N-dibutyl (meth) acrylamide, N
-Cyclohexyl (meth) acrylamide, (meth) acrylonitrile, styrene, 1-methylstyrene, vinyl acetate, vinyl alcohol, butadiene, vinyl chloride,
Isoprene, chloroprene, hydroxyethyl (meth)
Acrylate, diethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, (meth) acryloyloxy polyglycerol, vinyl alcohol, allyl alcohol, (meth) acrylamide, N-methyl (meth) acrylamide, N
-Methylol (meth) acrylamide, N-vinyl-2
-Pyrrolidone, vinylimidazole, N-methylol-
ε-caprolactam, N-methylolmaleimide, N-
Vinyl succinimide, p-aminostyrene, N-vinyl carbazole, 2-vinyl pyridine, 2-cyanoethyl (meth) acrylate, (meth) acrylic acid, (anhydride) maleic acid, fumaric acid, itaconic acid, vinyl sulfonic acid, (meth) ) Acrylic sulfonic acid, styrene sulfonic acid, vinyl benzoic acid, alkyl allyl sulfosuccinic acid,
(Meth) acryloyl polyoxyalkylene sulfate, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-diethylamino Propyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylamide, vinylaniline, 1,1,1-trimethylamine (meth) acrylimide, 1,1-dimethyl-1-
Ethylamine (meth) acrylimide, 1,1-dimethyl-1- (2′-phenyl-2′-hydroxyethyl)
Examples include amine (meth) acrylimide, 1,1,1-trimethylamine (meth) acrylimide, and the like, and combinations thereof.

As the resin latex (A), a latex of styrene-butadiene resin, styrene-acrylic resin, acrylic resin, vinyl acetate resin or ethylene-vinyl acetate resin is preferred.
Butadiene resin latex is preferred.

The resin content of the resin latex (A) is usually 2
0-75%, preferably 40-60%.

In the emulsion polymerization of the resin latex, known polymerization initiators and chain transfer agents are used. As the polymerization initiator, organic polymerization initiators [peroxides (cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramenthane hydroperoxide,
Benzoyl peroxide, lauroyl peroxide, etc.), azo compounds (azobisisobutyronitrile, azobisisovaleronitrile, etc.), inorganic polymerization initiators, persulfates (sodium persulfate, ammonium persulfate,
Potassium persulfate, etc.) and the like. The amount of the polymerization initiator to be used is usually 0.01 to 5% by weight based on the resin component.

In the present invention, a known chain transfer agent can be used for the purpose of adjusting the molecular weight of the resin, the gel content of the latex, and the like. As the chain transfer agent, α-methylstyrene dimer (2,4-diphenyl-4-methyl-
1-pentene), terpinolene, terpinene, dipentene, alkyl mercaptan having 8 to 18 carbon atoms, alkylene dithiol having 8 to 18 carbon atoms, alkyl thioglycolate, dialkyl xanthogen disulfide, tetraalkyl thiuram disulfide, carbon tetrachloride, etc. No. These can be used alone or in combination of two or more. The amount of the chain transfer agent to be used is generally 0 to 15 parts by weight based on 100 parts by weight of the monomer mixture.

The reducing agent [sodium pyrobisulfite,
Sodium sulfite, sodium hydrogen sulfate, ferrous sulfate,
Glucose, sodium formaldehyde sodium sulfoxylate, L-ascorbic acid (salt)], chelating agents (glycine, alanine, sodium ethylenediaminetetraacetate, etc.), pH buffers (sodium tripolyphosphate, potassium tetrapolyphosphate, etc.). It may be contained during emulsion polymerization.

In the present invention, the resin latex (A)
Means that the glass transition temperature of the resin component is usually -20 to 5
0 ° C, preferably -10 to 10 ° C. If the glass transition temperature is lower than −20 ° C., the strength of the coated paper is insufficient, and if it exceeds 50 ° C., the film-forming property is poor and the strength of the coated paper is insufficient. Here, the glass transition temperature refers to a differential scanning calorimeter (DSC) in which a latex is poured into a glass mold, dried at 30 ° C. and 10 mmHg or less for 8 hours and stored in a desiccator to form a film having a thickness of about 0.3 mm. ) Under nitrogen at 20 ° C./min. The glass transition temperature of the resin can be adjusted by the monomer composition of the resin.

The gel content of the resin latex (A) in the present invention is preferably 70 to 95% by weight, particularly preferably 75 to 95% in terms of improving the strength of the coated paper.
What is used is about 90% by weight. Here, the gel content means that about 1 g of latex was poured into a glass mold, dried at room temperature to form a film having a thickness of about 0.3 mm, and the solid content (gel) remaining after Soxhlet extraction with toluene was performed.
Is expressed as a percentage of the weight of the residue obtained by drying the latex at 130 ° C.

The gel content can be adjusted by adjusting the monomer composition of the resin, the type and amount of the polymerization initiator and the chain transfer agent used, and the like. In general, the amount of monomers having a plurality of radically polymerizable double bonds (butadiene, isoprene, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, divinylbenzene, etc.) is small. Then, the gel content decreases, and the gel content decreases as the amounts of the polymerization initiator and the chain transfer agent increase. Further, when peroxides or persulfates are used as the polymerization initiator, the gel content increases,
The use of a polyfunctional polymerization initiator and a chain transfer agent also increases the gel content.

The vinyl polymer (B) is preferably a polymer which sharply gels when an aqueous solution or aqueous suspension thereof is heated, and is preferably a vinyl amine of an alkylene oxide adduct of a cyclic amine or an acyclic amine having 5 or more carbon atoms. Polymer (B1) composed of carboxylic acid ester (b), polymer (B2) composed of N-alkyl or N-alkylene (meth) acrylamide, polyalkylene glycol monoalkyl ether mono (meth) acrylate or polyalkylene glycol monophenyl It is selected from the group consisting of a polymer (B3) composed of ether mono (meth) acrylate, a polymer (B4) composed of polyalkylene glycol monoalkyl monovinyl ether, and a polymer (B5) composed of polyalkylene glycol monophenyl monovinyl ether. Among these, the polymer is highly effective in suppressing the transfer of the resin latex particles to the surface of the coating color during heating and drying, and a coated paper having high air permeability and good blister resistance is obtained. (B1) is preferred.

The cyclic amine in the vinyl carboxylate (b) is not particularly limited as long as it is a cyclic amine having an active hydrogen for the addition of an alkylene oxide, and thus has an amine nitrogen inside and outside the ring. Just do it. The active hydrogen group may be derived from an amino group, or may be derived from any group to which an alkylene oxide can be added, such as a hydroxyl group or a carboxyl group.

Examples of such a cyclic amine include, for example,
Non-aromatic heterocyclic amine [having an aziridine ring (aziridine, 2-methylaziridine, 2-
Those having a pyrrolidine ring (e.g., pyrrolidine, 2-methylpyrrolidine, 2-ethylpyrrolidine, 2-pyrrolidone, succinimide, 1,2-cyclohexanedicarboximide), those having a piperidine ring (piperidine, 2- Methylpiperidine,
3,5-dimethylpiperidine, 2-ethylpiperidine,
4-piperidinopiperidine, 2-methyl-4-pyrrolidinopiperidine, ethylpicoliconate, etc., those having a piperazine ring (1-methylpiperazine, 1-methyl-3-ethylpiperazine, etc.), and a morpholine ring (Morpholine, 2-methylmorpholine, 3,
5-dimethylmorpholine, thiomorpholine, etc.),
Pyrolines (such as 3-pyrroline, 2,5-dimethyl-3-pyrroline, 2-phenyl-2-pyrroline), pyrazolines (such as pyrazoline), imidazoles (2-methylimidazole, 2-ethyl-4-methylimidazole) ,
2-phenylimidazole, pyrazoles (pyrazole, pyrazolecarboxylic acid, etc.), pyridones (α
-Pyridone, [gamma] -pyridone, etc.) and [epsilon] -caprolactam, pyridazinone, pyridalin, pyridoin, etc.]; aromatic heterocyclic amines [2-hydroxypyridine, 2-hydroxy-3,5-ditert-butylpyridine, 2-carboxyl] Pyridine, 4-pyridylcarbinol, 2-hydroxypyrimidine, pyrrole, 2-phenylpyrrole, etc.]; aromatic amines [aniline, 3-methylaniline, N-methylaniline, N-
Isopropylaniline and the like].

Among these cyclic amines, preferred are non-aromatic cyclic amines. Of these, those having a piperidine ring and those having a morpholine ring are most preferable, and those having a morpholine ring are most preferable.

The non-cyclic amine having 5 or more carbon atoms in (b) is not particularly limited as long as it is a non-cyclic amine having 5 or more carbon atoms having an active hydrogen for adding an alkylene oxide. For example, primary aliphatic acyclic amines having 5 or more carbon atoms (dimethylpropylamine, 2-ethylbutylamine, pentylamine, 2,2-dimethylbutylamine,
Hexylamine, cyclohexylamine, octylamine, 2-ethylhexylamine, isodecylamine, laurylamine, etc.), a secondary aliphatic acyclic amine having 5 or more carbon atoms [methylbutylamine, methylisobutylamine, methyl tert-butylamine, methyl Pentylamine, methylhexylamine, methyl (2-ethylhexyl) amine, methyloctylamine, methylnonylamine, methylisodecylamine, ethylpropylamine, ethylisopropylamine, ethylbutylamine,
Ethyl isobutylamine, ethyl tert-butylamine, ethylpentylamine, ethylhexylamine, ethyl (2-ethylhexyl) amine, ethyloctylamine, dipropylamine, diisopropylamine, propylbutylamine, propylisobutylamine, propyltertiarybutylamine, propylpentylamine ,
Propylhexylamine, propyl (2-ethylhexyl) amine, propyloctylamine, isopropylbutylamine, isopropylisobutylamine, isopropyltert-butylamine, isopropylpentylamine, isopropylhexylamine, isopropyl (2
-Ethylhexyl) amine, isopropyloctylamine, dibutylamine, diisobutylamine, ditertiarybutylamine, butylpentylamine, dipentylamine, dicyclohexylamine, etc.].

Preferred among the acyclic amines having 5 or more carbon atoms are primary aliphatic acyclic amines having 5 to 8 carbon atoms.

Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide and the like. Preferred among these are ethylene oxide or propylene oxide, and combinations of both.

The number of moles of the alkylene oxide added is usually 1 to 50 mol, preferably 1 to 5 mol.

(B) is a cyclic amine or a compound having 5 carbon atoms.
An ester of the above alkylene oxide adduct of an acyclic amine with a vinyl carboxylic acid. The vinyl carboxylic acid does not need to have a vinyl group and a carboxyl group directly linked, and may be, for example, a radical polymerizable unsaturated fatty acid such as (meth) acrylic acid, (iso) crotonic acid, maleic acid, fumaric acid, and itaconic acid. Aromatic carboxylic acids; radically polymerizable aromatic carboxylic acids such as vinylbenzoic acid and 2-carboxy-4-isopropenyl-3-pyrrolidineacetic acid; and ester-forming derivatives (acid anhydrides or acid halides) thereof. .

Of these, (meth) acrylic acid, maleic acid, vinylbenzoic acid and ester-forming derivatives thereof are preferred, and (meth) acrylic acid and (meth) acrylic acid
Ester-forming derivatives of acrylic acid are particularly preferred.

The polymer (B1) may be a polymer of vinyl carboxylate (b) or a copolymer of (b) and another vinyl monomer (c). It is necessary to contain 50% by weight or more. Preferably,
The content is 70% by weight or more.

Other vinyl monomers (c) include:
(C-1) hydrophilic (excluding (b)), (c-2)
It may be of a lipophilic vinyl monomer.

As (c-1), nonionic compounds [hydroxyethyl (meth) acrylate, diethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, (meth) acryloyloxy polyglycerol, vinyl alcohol, allyl Alcohol, (meth) acrylamide, N-methyl (meth) acrylamide, N-methylol (meth) acrylamide, N-vinyl-2-pyrrolidone, vinylimidazole, N-methylol-ε-caprolactam, N-
Methylol maleimide, N-vinyl succinimide, p
-Aminostyrene, N-vinylcarbazole, 2-vinylpyridine, 2-cyanoethyl (meth) acrylate, etc.]; anionic compound [(meth) acrylic acid, (anhydride) maleic acid, fumaric acid, itaconic acid, vinylsulfonic acid , (Meth) acrylic sulfonic acid, styrene sulfonic acid, vinyl benzoic acid, alkyl allyl sulfosuccinic acid,
Acids such as (meth) acryloyl polyoxyalkylene sulfate and salts thereof]; cationic compounds [N,
N-dimethylaminoethyl (meth) acrylate, N,
N-dimethylaminopropyl (meth) acrylate,
N, N-diethylaminoethyl (meth) acrylate,
N, N-diethylaminopropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylamide, vinylaniline and acid salts thereof]; Compound having an amineimide group [1,1,1-trimethylamine (meth) acrylimide] , 1,1-dimethyl-1-ethylamine (meth) acrylimide, 1,1-dimethyl-
1- (2'-phenyl-2'-hydroxyethyl) amine (meth) acrylimide, 1,1,1-trimethylamine (meth) acrylimide, etc.].

As (c-2), for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, octadecyl (meth) acrylate, glycidyl (Meth) acrylate derivatives such as (meth) acrylate, N-alkyl (meth) acrylamide derivatives such as N, N-dibutyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, (meth) acrylonitrile, styrene,
Examples include 1-methylstyrene, vinyl acetate, butadiene, vinyl chloride, isoprene and the like.

The vinyl polymer (B1) can be obtained, for example, by the method described in JP-A-6-9848.

Examples of the polymer (B2) include (co) polymers of N-alkyl or N-alkylene (meth) acrylamide monomers and copolymers of the monomers with the other vinyl monomers (c). .

Specific examples of the N-alkyl or N-alkylene (meth) acrylamide monomer constituting the polymer (B2) include N-ethyl (meth) acrylamide,
N, N-diethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, Nn-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-cyclopropyl (meth) acrylamide, N- ( (Meth) acryloylpiperidine, N- (meth) acryloylpyrrolidine, N- (meth) acryloylhexahydroazene, (meth) acryloylmorpholine, N-tetrahydrofurfuryl (meth) acrylamide, N-methoxypropyl (meth) acrylamide, N
-Ethoxypropyl (meth) acrylamide, N-isopropoxypropyl (meth) acrylamide, N-ethoxyethyl (meth) acrylamide, N- (2,2-dimethoxyethyl) -N-methyl (meth) acrylamide, N-1- Methyl-2-methoxyethyl (meth) acrylamide, N-1-methoxymethylpropyl (meth)
Acrylamide, N- (1,3-dioxolan-2-yl) -N-methyl (meth) acrylamide, N-8-acryloyl-1,4-dioxa-8-aza-spiro [4,5] decane, or N -Methoxyethyl-N-
n-Propyl (meth) acrylamide.

The polymer (B2) is described, for example, in JP-A-1-1-1.
It is obtained by the method described in JP-A-4276.

As the ω-alkoxypolyalkylene glycol mono (meth) acrylate or ω-phenoxypolyalkylene glycol mono (meth) acrylate constituting the polymer (B3), (meth) acrylic acid of ethylene oxide adduct of monohydric alcohol is used. Ester [ω-methoxy polyethylene glycol mono (meth) acrylate, ω-ethoxy polyethylene glycol mono (meth)
Acrylate, ω-propoxy polyethylene glycol mono (meth) acrylate, ω-butoxy polyethylene glycol mono (meth) acrylate, ω-cyclohexyl polyethylene glycol mono (meth) acrylate, ω-phenoxy polyethylene glycol mono (meth) acrylate, etc.], monovalent (Meth) acrylic acid ester of ethylene oxide adduct of propylene oxide adduct of alcohol [ω-methoxy (poly) oxypropylene polyoxyethylene mono (meth) acrylate etc.],
(Meth) acrylic acid ester of propylene oxide adduct of monohydric alcohol ethylene oxide adduct [ω-methoxypolyoxyethylene (poly) oxypropylene mono (meth) acrylate etc.] Ethylene oxide addition of monohydric alcohol propylene oxide adduct (Meth) acrylate of propylene oxide adduct of the product [ω
-Methoxy (poly) oxypropylene polyoxyethylene (poly) oxypropylene mono (meth) acrylate, etc.) or (meth) acrylic acid ester of ethylene oxide adduct of ethylene oxide adduct of monohydric alcohol with propylene oxide adduct [ω- Methoxypolyoxyethylene (poly) oxypropylene polyoxyethylene mono (meth) acrylate, etc.]. The polyoxyalkylene polymerization degree in the polyalkylene glycol mono (meth) acrylate is 2 to 50. Examples of the polymer (B3) include one or more of these mono (meth) acrylate (co) polymers and copolymers with comonomers. The same comonomer as the vinyl monomer (c) can be used.

The polymer (B3) is described, for example, in JP-A-6-2
It can be obtained by the method described in JP-A-3375.

The polyalkylene glycol monoalkyl monovinyl ether constituting the polymer (B4) includes
Vinyl ether obtained from ethylene oxide adduct of monohydric alcohol and vinyl chloride (polyethylene glycol monoethyl monovinyl ether, polyethylene glycol monopropyl monovinyl ether, polyethylene glycol monobutyl monovinyl ether, etc.) and propylene oxide / ethylene oxide adduct of monohydric alcohol Vinyl ether obtained from vinyl chloride [(poly)
Oxypropylene polyoxyethylene glycol monomethyl monovinyl ether] and (poly) oxyethylene (poly) oxypropylene polyoxyethylene glycol monomethyl monovinyl ether].
Examples of the polyalkylene glycol monophenyl monovinyl ether constituting the polymer (B5) include vinyl ethers (eg, polyethylene glycol monophenyl monovinyl ether) obtained from ethylene oxide adducts of phenols and vinyl chloride. The polyoxyalkylene polymerization degree in the polyalkylene glycol monovinyl ether is 2 to 50.

As the polymer (B4) or (B5),
One or more of these monovinyl ethers include (co) polymers and copolymers with comonomers. As the comonomer, the same as the above-mentioned vinyl monomer (c) can be used.

The polymer (B4) or (B5) is described, for example, in Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 30, page 2407 (1992).
Obtained by the method described in (1).

The weight average molecular weight of the vinyl polymer (B) is generally 1,000 to 5,000,000, preferably 1
000 to 2,000,000, particularly preferably 10
It is between 000 and 1,000,000.

In the binder composition of the present invention,
The ratio of (A) and (B) is usually 70-9 based on weight.
9.99: 0.01 to 30, preferably 80 to 99.
5: 0.05 to 20. When the proportion of (B) is less than 0.01% by weight, the obtained coated paper has insufficient blister resistance.

The binder composition of the present invention is obtained by converting a resin latex (A) and a vinyl polymer (B) alone or a mixture obtained by diluting (B) with water from the hydrophilic property of the vinyl polymer (B) to the hydrophobic property. At a temperature lower than the temperature at which it changes with a conventional mixing device (such as a paddle-type stirring blade).

The binder composition of the present invention may be used, if necessary, for the purpose of increasing the adhesion to paper or increasing the water retention of the coating color, for example, by cationizing starch, oxidized starch, casein, and soy protein. And known water-soluble compounds used for coating colors such as synthetic proteins, polyvinyl alcohol, maleic anhydride resins, carboxymethyl cellulose, and hydroxyethyl cellulose.

If necessary, various clays, kaolin, calcium carbonate, satin white, titanium oxide, aluminum hydroxide, barium sulfate, zinc oxide, calcium sulfate, talc, plastic pigment (polystyrene, styrene / butadiene copolymer) Or styrene /
One or more known pigments used for coating colors such as beads such as acrylic copolymers) can be contained.

Further, if necessary, a pigment dispersant [sodium poly (meth) acrylate, sodium pyrophosphate, sodium hexametaphosphate, etc.] and an antifoaming agent (mineral oil-based antifoaming agent, silicon-based antifoaming agent, etc.) , And other additives [lubricants, pH adjusters, preservatives, water-proofing agents, printability improvers, etc.].

A method for producing a coating color using the binder composition of the present invention will be described. First, a pigment is dispersed in water using a dispersing device in the presence of a pigment dispersant and an antifoaming agent to obtain a pigment slurry. Next, a water-soluble binder dissolved in water is added, and after homogenization, a coating color is obtained by blending the coated paper binder of the present invention and other additives. Examples of the dispersing device include a high-speed mixer, a Keddy mill, a speed mill, a sigma blade kneader, a more house mill, and a lead kneader.

A method for producing a coated paper using a coating color containing the binder composition of the present invention will be described.
Coated paper is usually coated using a coating machine using base paper for coating (high quality paper,
It is obtained by applying a coating color to medium-grade paper and lower-grade paper, drying with a drier, and smoothing finish.

The coating is performed by a coating machine in one or more layers. Coating machines include roll coaters (size presses, gate roll coaters, etc.), double-sided simultaneous coating type coaters (build blade coaters, twin blade coaters, etc.), various blade coaters (bench type coaters, helicopters, etc.), air knife coaters , A rod coater, a brush coater, a curtain coater, a chaplex coater, a bar coater, a gravure coater and the like. As a coating machine, a blade coater capable of high-speed coating is preferable. Coating speed is usually 1 to
It is 5000 m / min, preferably 500 to 5000 m / min. The coating amount is usually 1 to 50 g / weight as a weight after drying.
m2, preferably 5 to 25 g / m2.

Drying is performed by steam heating, hot air heating, gas heater heating, electric heater heating, infrared heater heating, near infrared heater heating, high frequency heating, laser heating, electron beam heating, or the like. As the dryer, infrared dryer, drum dryer, air cap dryer, air foil dryer, air conditioner bear dryer,
And combinations thereof. As the dryer, a combination of an infrared dryer, an air cap dryer, and an air foil dryer capable of high-speed drying is preferable.

The drying temperature varies depending on the type of dryer, but the temperature inside the dryer is usually 50 to 1500.
° C.

The smoothing finish can be performed by using a normal calendar (super calendar, gloss calendar, soft calendar, machine calendar, etc.) on-machine or off-machine. The processing pressure and temperature are not particularly limited, and the nip pressure is usually 20 to 50.
The reaction is carried out at 0 kg / cm, usually at room temperature to 500 ° C. The number of pressure nips is usually 1 to 15. In addition, a water application device using a roll, an electrostatic humidification device, a steam humidification device, or the like can be installed together with the calender for humidity control and humidification of the processed paper after finishing.

[0059]

EXAMPLES The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples. Parts in the examples are parts by weight. Production Example 1 100 parts of 2-morpholinoethyl methacrylate (an ester of morpholine with one mole of ethylene oxide and methacrylic acid) and 0.1 part of 2,2′-azobis (2,4-dimethylvaleronitrile) were added to an ampoule. After freezing and deaeration, the system was sealed and polymerized at 50 ° C. for 8 hours to obtain a polymer 1.

Production Example 2 90 parts of 2- (2-morpholinoethoxy) ethyl methacrylate (2 mol adduct of morpholine with ethylene oxide, ester with methacrylic acid), 10 parts of methyl methacrylate and 2,2′-azobis (2,2 0.1 part of 4-dimethylvaleronitrile) was added to the ampoule, frozen, degassed, sealed, and polymerized at 60 ° C. for 8 hours to obtain a polymer 2.

Production Example 3 80 parts of 2-morpholinopropyl methacrylate (ester of methacrylic acid with 1 mol of propylene oxide adduct of morpholine), 5 parts of styrene, 10 parts of methyl methacrylate, 5 parts of hydroxyethyl methacrylate and 2,2 ′ -Add 0.1 part of azobis (2,4-dimethylvaleronitrile) to the ampoule, freeze, deaerate and seal.
Polymerization was performed at 0 ° C. for 8 hours to obtain a polymer 3.

Production Example 4 80 parts of 2- (2-piperidinoethoxy) ethyl methacrylate, 10 parts of N, N-dibutylacrylamide, 10 parts of styrene and 2,2′-azobis (2,4-dimethylvaleronitrile) 0 0.5 part was added to an ampoule, frozen, degassed, sealed, and polymerized at 50 ° C. for 8 hours to obtain a polymer 4.

Production Example 5 An ampoule was added with 80 parts of an acrylic acid ester of a 4 mol addition product of dimethylpropylamine with ethylene oxide, 20 parts of methyl methacrylate and 0.5 part of 2,2'-azobis (2,4-dimethylvaleronitrile). After freezing and degassing, the mixture was sealed and polymerized at 50 ° C. for 8 hours to obtain a polymer 5.

Production Example 6 In a pressurized reaction vessel equipped with a stirrer, a dropping cylinder, a nitrogen gas inlet tube and a thermometer, 10 parts of acryloyloxypolypropylene (degree of polymerization = 12) sulfate as an emulsifier having a radical polymerizable group, water 102 Parts, 45 parts of styrene, 9 parts of methyl methacrylate, 4 parts of methacrylic acid, 1 part of sodium persulfate and 0.2 part of lauryl mercaptan, and the system was purged with nitrogen gas under stirring, and then 37 parts of butadiene was added from a dropping cylinder. Press in, 50 ° C for 30 hours, 85 ° C
For 5 hours. PH with aqueous sodium hydroxide solution
The mixture was adjusted to 8.5, and the unreacted monomer was stripped under reduced pressure to obtain SBR-based resin latex 1 (solid content: 47.9%, hereinafter referred to as SBR1). SBR1
The emulsifier amount of the aqueous phase was 0.0003 mmol / g (resin), the gel content was 84%, and the glass transition temperature was -8 ° C.

Production Example 7 In the same manner as in Production Example 6, 50 parts of styrene, 4 parts of methyl methacrylate, 4 parts of methacrylic acid, and 5 parts of acrylonitrile
Parts, butadiene 32 parts and methacryloyloxy polyoxypropylene (degree of polymerization = 9) sulfate Na salt 10
Part, SBR resin latex 2 (solids 48.3)
%, Hereinafter referred to as SBR2). The emulsifier amount of the aqueous phase of SBR2 was 0.0005 mmol / g (resin), the gel content was 87%, and the glass transition temperature was 1 ° C.

Production Example 8 An SBR for comparison was prepared in the same manner as in Production Example 6 except that 10 parts of sodium alkyldiphenyl ether disulfonate [Eleminol MON-7 manufactured by Sanyo Chemical Industries, Ltd.] was used as an emulsifier.
Resin latex 3 (solid content 48.2%, hereinafter SBR3
). The amount of emulsifier in the aqueous phase of SBR3 is 0.1
mmol / g (resin), the gel content was 83%, and the glass transition temperature was -8 ° C.

Production Example 9 SBR resin latex 4 for comparison (solid content) was prepared in the same manner as in Production Example 6 except that 32 parts of styrene was used instead of 45 parts of styrene and 50 parts of butadiene were used instead of 37 parts of butadiene. 48.2%, hereinafter referred to as SBR4). The emulsifier amount of the aqueous phase of SBR4 is 0.0004 mmol
1 / g (resin), the gel content was 77%, and the glass transition temperature was -30 ° C.

Examples 1 to 5, Comparative Examples 1 and 2 25 parts of water, 0.3 part of dispersant [SN Dispersant 5040 manufactured by San Nopco Co., Ltd.], 0.1 part of sodium hydroxide
Part, antifoaming agent [San Nopco Co., Ltd. Nopco DF122]
7. 0.1 part, 35 parts of clay and 15 parts of calcium carbonate are dispersed and mixed at 2,000 rpm for 30 minutes by a disper, and the resulting dispersion is pre-gelatinized phosphorylated starch (30% aqueous solution).
3 parts, 0.07 of a 40% aqueous solution of the polymer 1 obtained in Production Example 1
And 14.1 parts of a binder composition 1 obtained by mixing 14 parts of SBR1 obtained in Production Example 6 with 14 parts of SBR1 were added and uniformly mixed to obtain Coating Color 1 of Example 1. In the same manner as described above, the coating color 2 of Example 2 was prepared using the binder composition 2 prepared by mixing the polymer 2 and SBR1, and the coating color 2 of Example 3 was prepared using the polymer 3 and SBR2. Coating color 3
Coating color 4 of Example 4 using polymer 4 and SBR2
To obtain a coating color 5 of Example 5 using the polymer 5 and SBR1. A coating color 6 of Comparative Example 1 was obtained using Polymer 1 and SBR3, and a coating color 7 of Comparative Example 2 was obtained using SBR4 and Polymer 1.

Each of the coating colors 1 to 7 was coated on a medium paper of 58 g / m 2 at a dry coating amount of about 10 g / m 2 using a bar coater on one side, and then dried in a circulating drier at 150 ° C. for 30 seconds. After drying, the other side was similarly coated, dried and cut. afterwards,
The coated papers 1 to 7 were prepared by processing (temperature: 60 ° C., nip pressure: 90 kg / cm, once on each side of the paper passing) using a mini super calender, and various physical properties of each coated paper were measured. Table 1 shows the results
Shown in

[0070]

[Table 1]

Printing test: Offset ink was solid-coated with an RI printing machine manufactured by Akira Seisakusho Co., Ltd. Gloss: 75 ° gloss was measured with a gloss meter manufactured by Tokyo Denshoku Co., Ltd. Traffic: The degree of picking of the printed surface was visually determined with an ink for picking test using an RI printing machine. 5 is the best level on a 5-point scale. Blister resistance; solid coated with offset ink on both sides of coated paper with RI printing machine, humidified at 25 ° C and 60% humidity for 24 hours, quickly immersed in temperature-controlled silicone oil, and checked for blistering Was visually determined. The lowest temperature at which blistering occurred.

[0072]

The binder composition for producing a coated paper for rotary offset printing of the present invention is coated with a rotary offset printing paper excellent in blister resistance even in a coating method other than the curtain coating method (such as a blade coater). Can be used for top-coating of single-coated paper or double-coated paper.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C09D 171/02 C09D 171/02 201/00 201/00

Claims (4)

(57) [Claims] 1. The amount of an emulsifier in an aqueous phase is 0.01 mmol /
g (resin) or less, and the glass transition temperature of the resin is −20.
A resin latex (A) having a temperature of ５０50 ° C. and the following (B1)
A rotatable offset characterized by containing a vinyl polymer (B) whose hydrophilicity and hydrophobicity change reversibly at a certain temperature selected from the group consisting of the group consisting of Binder composition for producing coated paper for printing. (B1): a polymer comprising a vinyl carboxylate (b) of an alkylene oxide adduct of a cyclic amine or an acyclic amine having 5 or more carbon atoms, (B2): an N-alkyl or N-alkylene (meth)
(B3): a polymer comprising polyalkylene glycol monoalkyl ether mono (meth) acrylate or polyalkylene glycol monophenyl ether mono (meth) acrylate; (B4): a polymer comprising polyalkylene glycol monoalkyl monovinyl ether (B5): a polymer comprising polyalkylene glycol monophenyl monovinyl ether. 2. The composition according to claim 1, wherein (A) is a resin latex synthesized using an emulsifier (a) having a (meth) acryloyl group. 3. The composition according to claim 1, wherein (A) is a styrene-butadiene resin latex having a gel content of 70 to 95% by weight. 4. A coated paper for rotary offset printing, comprising a coated layer formed from the composition according to claim 1.