JP3515843B2 - Latex-like polymer composed of fine particles having heterogeneous structure - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material.
Latex-like poly useful for paints, paints, adhesives, etc.
About ma. [0002] Active methylene groups are amino groups, isocyanate groups.
Reacts with salts, melamine, etc. to form covalent bonds.
Ethylenically unsaturated with an active methylene group
For monomers, homopolymerization or various ethylene
Formed by performing copolymerization with a reactive unsaturated monomer.
Various applications of polymers having a reactive group in the side chain
Has been disclosed. For example, Japanese Patent Publication No. 45-5819
No. 46-22507, JP-A-50-73625
In photographic photosensitive materials, 2-acetoacetoxyethyl
Methacrylate or 2-cyanoacetoxyethyl methacrylate
A monomer having an active methylene group such as
Polymer latte copolymerized with monomers such as acrylate
Coexisting in the gelatin film
Abrasion resistance (especially in the wet state)
It is disclosed that the hardness is improved. But
The abrasion resistance of gelatin film by these latex,
Active methylene monomer is required for the desired improvement in hardness.
It is necessary to copolymerize at least a certain amount. The ratio of latex to gelatin is
Higher or the absolute amount of gelatin is lower,
The strength of the gelatin film in the
Copolymerization of a large amount of active methylene monomer was required
It is necessary only to increase the amount of active methylene monomer.
There was a problem that the film strength could not be obtained. Therefore, low
Add gelatin coated film or a large amount of latex
In conventional gelatin films, conventional active
In some cases, film strength improvement is not sufficient in len monomer copolymerization.
Active methylene mono, which has a relatively complex structure
Of polymer latex by using a large amount of polymer
Problems such as increased production costs, and further improvements are desired
Was. Also, JP-A-5-295302, European Patent Publication
No. 501666, International Patent Publication No. 93-16133, etc.
Is an active methylene monomer as a latex for paint
Excellent in water resistance, salt water resistance, alkali resistance, etc.
The characteristics are shown in JP-A-4-253784,
5-194914, 5-287248, European Patent
Publication No. 573142 and the like disclose the activity as an adhesive latex.
Adhesive strength and water resistance
It is disclosed that it shows excellent characteristics in terms of properties and the like. "Toshihiko Nakamichi, Coloring Materials, Vol. 65, 511-5
25 (1992) ", an active methylene monomer
Copolymers can be three-dimensionally crosslinked by co-use with various additives.
It is described that a film is formed, and the above-mentioned coating and bonding
The effect of active methylene monomer copolymerization in the field of
This can be understood by the crosslinking reaction. However,
In the field, with the same amount of active methylene monomer,
Material technology that expresses excellent characteristics is also considered in terms of performance
It is also desired from an economic point of view. On the other hand, core / shell
As a polymer latex having a double structure,
Japanese Patent Application Laid-Open No. 58-42044 discloses that a shell part is a developing agent acid.
Couplers that can form dyes by coupling with
Core / shell latec made of polymer containing silica
Silver halide color photographic light-sensitive material containing silver halide
Among them, specifically, as a yellow coupler,
Valoylacetoanilide type or benzoylacetoa
A nilide type is described. [0005] However, the co-
A / shell polymer latex has the following problems
There is. Extremely low percentage of cores composed of non-color-forming monomers
No (at most about 10% of the exemplified compounds). Therefore,
Active methylene moiety is collected on the shell side by core / shell conversion
The above-mentioned various merits by being set inside are small. Po
In the field of remer couplers, coupler monomer units
It is necessary to increase the number of knits as much as possible.
Considering that it is advantageous in terms of
Extremely inadequate. Pivaloylacetanilide or benzoylacetate
A three-dimensional crowded activity such as toanilide
The reactivity of the reactive methylene structure is not always sufficient,
For example, in view of the effect of improving the strength of gelatin film,
Good is desired. The patent also discloses that conjugated diene is used as a core particle.
The use of enmonomer and its usefulness
Not listed. [0006] The first object of the present invention
Is a polystyrene containing an active methylene monomer having a novel structure
To provide mer latex. The second of the present invention
The purpose is a gelatin / latex composite film with excellent film strength.
Film, paint and adhesive composition with excellent water resistance and adhesive strength
The purpose of the present invention is to provide a useful polymer latex. [0007] The above object of the present invention is to achieve a common object.
Having a repeating unit derived from a diene monomer
Rimmer core and at least one active methylene group
Derived from ethylenically unsaturated monomers having phenol
Composed of a shell made of a polymer having
Latex-like particles composed of fine particles having a heterogeneous structure.
Achieved by Rimmer. In a preferred embodiment of the present invention
The weight ratio of each polymer of the core and the shell is 20/80.
To 95/5. Another preferred embodiment of the present invention
In some embodiments, ethylenically unsaturated groups having an active methylene group
The sum monomer is a monomer represented by the following general formula (I)
It is characterized by that. General formula (I) CH _Two = C (R ¹ ) -LX where R ¹ Is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or
Represents a halogen atom, L represents a single bond or a divalent linking group
Represents X is R ^Two COCH _Two COO-, NC-CH _Two COO-, R ^Two COCH _Two CO
-, NC-CH _Two CO- (R ^Two Is substituted or unsubstituted having 1 to 12 carbon atoms
Substituted alkyl group, substituted or unsubstituted having 6 to 20 carbon atoms
An aryl or aryloxy group having 1 to 12 carbon atoms
An alkoxy group, an amino group, a substituted amino group having 1 to 12 carbon atoms
R) ⁹ -CO-CH _Two CON (R ⁶ )-(R ⁶ Is a hydrogen atom,
Represents a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms,
R ⁹ Is a substituted or unsubstituted primary or non-substituted C 1-12 or
Secondary alkyl group, alkoxy group having 1 to 12 carbon atoms,
A substituted amino group having 1 to 12 carbon atoms)
L is not a single bond, L is
Alkylene, aralkylene or aryle for X
Join in the form of Hereinafter, for the sake of simplicity, the heterophasic structure of the present invention
Latex-like polymer consisting of fine particles having
Called polymer latex or / core-shell latex
Huh. Hereinafter, the polymer latex of the present invention will be described.
This will be described in detail. The polymer latex of the present invention has a core
/ Polymeric latex of different phase structure composed of shell
Yes, the core is a repeat derived from a conjugated diene monomer
It is a polymer having units. Has a conjugated diene structure
Preferred examples of the monomer include 1,3-butadiene and i.
Soprene, 1,3-pentadiene, 2-ethyl-1,3
-Butadiene, 2-n-propyl-1,3-butadiene
, 2,3-dimethyl-1,3-butadiene, 2-methyl
1,3-pentadiene, 1-phenyl-1,3-bu
Tadiene, 1-α-naphthyl-1,3-butadiene, 1
-Β-naphthyl-1,3-butadiene, 2-chloro-
1,3-butadiene, 1-bromo-1,3-butadiene
, 1-chlorobutadiene, 2-fluoro-1,3-butane
Tadiene, 2,3-dichloro-1,3-butadiene,
1,1,2-trichloro-1,3-butadiene and 2-
Cyano-1,3-butadiene can be mentioned. This
Among them, 1,3-butadiene, isoprene, 2-
Roll-1,3-butadiene is particularly preferred. Further, the core of the latex of the present invention is constituted.
As the polymer, a polymer other than the conjugated diene monomer described above is used.
Nomers may be copolymerized. Such a monomer
Examples of ethylene, propylene, 1-butene, i
Sobutene, styrene, α-methylstyrene, divinylbenzene
Monoethylenic unsaturated of benzene, vinyl ketone and aliphatic acid
Japanese hydrocarbon (alkene) esters (eg, vinyl acetate,
Allyl acetate), ethylenically unsaturated monocarboxylic acid
Or dicarboxylic acid esters (eg, methyl methacrylate
, Ethyl methacrylate, n-butyl methacrylate
G, n-hexyl methacrylate, cyclohexyl meth
Acrylate, benzyl methacrylate, n-butyl acrylate
Relate, n-hexyl acrylate, 2-ethylhexyl
Sil acrylate, t-butyl methacrylate, dodeci
Lemethacrylate, 2-hydroxyethyl acrylate
G, 2-hydroxyethyl methacrylate, 2-hydro
Xypropyl methacrylate, ethylene glycol dye
Tacrylate, ethylenically unsaturated monocarboxylic acid
Or amides of dicarboxylic acids (eg, t-butyl acryl)
Amide, t-butyl methacrylamide) and monoethylene
Unsaturated compounds (eg acrylonitrile, methacrylic
Ronitrile) and the like. [0010] Among them, ethylene, propylene, and ethylene
Tylene, α-methylstyrene, acrylic acid or meta
Ester of acrylic acid, acrylonitrile, methacrylonitrile
Tolyl is particularly preferred. Having the above conjugated diene structure
Two or more monomers and other copolymerized monomers
May be used. Polymerization of monomer having conjugated diene structure
As a result, the unsaturated structure introduced into the core polymer is
As is well known in the art, a cis-1,4 bond
Or a trans 1,4-bond or
It may be a 1,2-bond. As mentioned above, the core
Polymers are derived from monomers with a diene structure
It may be a homopolymer, or may be combined with another hydrophobic monomer.
It may be a copolymer. In the case of a copolymer, each monomer
Is a random copolymer in which is copolymerized at an arbitrary ratio
Or a block copolymer. Such a common
Regarding the polymer of the active diene monomer and the synthesis method, for example,
Shunsuke Murahashi et al. “Synthetic Polymer II, 1975, Asakura Shoten”
Issuance ”, pages 171 to 308. Preferred embodiments of the core polymer described above
Examples include styrene-butadiene copolymers (typically S
It is called BR, and there are solution polymerization SBR and emulsion polymerization SBR.
You. As the solution polymerization SBR, in addition to the random polymer,
The block copolymer (for example, butadiene-styrene)
Block copolymer, styrene-butadiene-styrene
Lock copolymer)), butadiene homopolymer (example)
For example, cis-1,4-butadiene, trans-1,2-butane
Tadiene or these and trans-1,4-pig
Rubber mixed with diene structure), isoprene homopolymer
(Example of three-dimensional structure is the same as for butadiene polymer), styrene
-Isoprene copolymer (random copolymer, block
Copolymer), ethylene-propylene-diene copolymer
(As diene monomers, 1,4-hexadiene, diene
Cyclopentadiene, ethylidene norbornene, etc.
Acrylonitrile-butadiene copolymer)
Coal, chloroprene copolymer, isobutylene-isoprene
Copolymer, butadiene-acrylate copolymer
(As acrylates, ethyl acrylate,
Butyl acrylate) and butadiene-acrylate
Ru-acrylonitrile copolymer (with acrylic acid ester)
Can be used as described above)
it can. The glass transition temperature of these core polymers
(Tg) is usually 50 ° C. or lower, particularly 20 ° C. or lower.
The proportion of the conjugated diene monomer component in the polymer
There is no particular limitation on the amount of
A range is preferred. Of the core polymers described above,
In a preferred embodiment, the polymer is produced by emulsion polymerization.
And derived from a monomer having a diene structure
Homopolymer (for example, butadiene, isoprene homopolymerization
) Or a copolymer thereof (eg, the above-mentioned SBR).
It is a dust (latex). Such dispersion
In products, the core polymer exists in the form of fine particles.
You. The particle size of this polymer is
Film physical properties, its own water dispersion stability, and film formation
And too large is not preferable. Above points
More preferably, the number average particle diameter of the core polymer is 1.0 μm or less.
0.7 μm or less, particularly preferably 0.5 μm or less.
You. And it is preferable that it is 0.0001 μm or more.
No. About the shell part of the core / shell latex of the present invention,
This will be described below. [0013] The shell portion of the present invention comprises at least one active material.
Ethylenically unsaturated monomers having a methylene group (active
Having repeating units derived from
It is a rimmer. Preferred active methylene monomer in the present invention
The nomer is represented by the following general formula (I). General formula (I) CH _Two = C (R ¹ ) -LX where R ¹ Is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or
Represents a halogen atom, L represents a single bond or a divalent linking group
Represents X is R ^Two COCH _Two COO-, NC-CH _Two COO-, R ^Two COCH _Two CO-
, NC-CH _Two CO- (R ^Two Is substituted or unsubstituted having 1 to 12 carbon atoms
Substituted alkyl group, substituted or unsubstituted having 6 to 20 carbon atoms
An aryl or aryloxy group having 1 to 12 carbon atoms
An alkoxy group, an amino group, a substituted amino group having 1 to 12 carbon atoms
R) ⁹ -CO-CH _Two CON (R ⁶ )-(R ⁶ Is a hydrogen atom,
Represents a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms,
R ⁹ Is a substituted or unsubstituted primary or non-substituted C 1-12 or
Secondary alkyl group, alkoxy group having 1 to 12 carbon atoms,
A substituted amino group having 1 to 12 carbon atoms)
Represents an active methylene group, and when L is not a single bond, L
Is an alkylene, aralkylene or aryl for X
Combine in the form of a len. R ¹ Is preferably a hydrogen atom, methyl,
, N-propyl, n-butyl, chlorine atom, bromine atom
Represents, particularly preferably a hydrogen atom, a methyl group, a chlorine atom
Represent. L represents a single bond or a divalent linking group, for example,
It is a linking group represented by the following formula. − (L ¹ ) M- (L ^Two ) N- where L ¹ Is -CON (R ^Three )-(R ^Three Is a hydrogen atom, carbon number 1
To 4 alkyl groups or substituted alkyl having 1 to 6 carbon atoms
Represents a group), -COO-, -NHCO-, -OCO-, (R ^Four , R ^Five Is independently hydrogen, hydroxyl,
Halogen atom or substituted or unsubstituted alkyl,
Represents alkoxy, acyloxy or aryloxy
Then R ^Three Is as defined above), and L ^Two Is L ¹ And X
And m represents 0 or 1, and n represents 0
Or represents 1. When n = 0, m = 0. L
^Two The linking group represented by, for example, also represented by the following general formula
It is. -X ¹ -(J ¹ -X ^Two ) p-(J ^Two -X ^Three ) q- (J ^Three -X ^Four ) r-J ¹ , J ^Two , J ^Three May be the same or different, and -CO
-, -SO _Two -, CON (R ⁶ )-(R ⁶ Is a hydrogen atom, an alkyl group (charcoal
Prime number 1-6), substituted alkyl group (carbon number 1-6)), -S
O _Two N (R ⁶ )-(R ⁶ Is as defined above), -N (R ⁶ ) -R ⁷ -(R ⁶ Is above
Synonymous with R ⁷ Is an alkylene group having 1 to about 4 carbon atoms), -N
(R ⁶ )-(R ⁷ ) -N (R ⁸ )-(R ⁶ , R ⁷ Is as defined above, R ⁸ Is water
Elemental atom, alkyl group (C1-6), substituted alkyl group
(Representing 1 to 6 carbon atoms)), -O-, -S-, -N (R ⁶ ) -CO-N
(R ⁸ )-(R ⁶ , R ⁸ Is as defined above), -N (R ⁶ ) -SO _Two -N (R ⁸ )
-(R ⁶ , R ⁸ Is as defined above), -COO-, -OCO-, -N
(R ⁶ ) CO _Two -(R ⁶ Is as defined above), -N (R ⁶ ) CO- (R ⁶ Is
The same as the above). p, q, and r represent 0 or 1.
You. X ¹ , X ^Two , X ^Three , X ^Four Are the same but different
May be unsubstituted or substituted having 1 to 10 carbon atoms.
Alkylene group, aralkylene group having 7 to 20 carbon atoms, and
Represents a phenylene group having 6 to 20 carbon atoms, and an alkylene group
May be linear or branched. Examples of the alkylene group include
Methylene, methylmethylene, dimethylmethylene, methoxy
Simethylene, dimethylene, trimethylene, tetramethyle
, Pentamethylene, hexamethylene, decylmethyle
And aralkylene groups such as benzylidene and
Examples of the nylene group include p-phenylene and m-phenylene
, Methylphenylene, chlorophenylene and the like. X is a monovalent group containing an active methylene group.
R ^Two COCH _Two COO-, NCCH _Two COO-, R ^Two COCH _Two CO-, NC-CH _Two C
O-, R ⁹ -CO-CH _Two CON (R ⁶ )-. Where R ⁶ Is the same as above
Righteous, R ^Two Is substituted or unsubstituted having 1 to 12 carbon atoms
(E.g., methyl, ethyl, n-propyl,
n-butyl, t-butyl, n-nonyl, 2-methoxy
Tyl, 4-phenoxybutyl, benzyl, 2-methanes
Such as rufonamidoethyl), substitution having 6 to 20 carbon atoms, or
Unsubstituted aryl groups (eg, phenyl, p-methyl
Nil, p-methoxyphenyl, o-chlorophenyl
Etc.), an alkoxy group having 1 to 12 carbon atoms (for example,
, Ethoxy, methoxyethoxy, n-butoxy, etc.),
A cycloalkyloxy group (eg, cyclohexyloxy)
(C) substituted or unsubstituted ants having 6 to 20 carbon atoms
-Roxy (for example, phenoxy, p-methylphenoxy,
o-chlorophenoxy, p-cyanophenoxy, etc.)
Amino group, a substituted amino group having 1 to 12 carbon atoms (for example, methyl
Amino, ethylamino, dimethylamino, butylamino
, Dichlorophenylamino, etc.). Mentioned above
Particularly preferred R ^Two Is a C 1-12 substituted or
Is an unsubstituted primary or secondary alkyl group. R ⁹ Is
A substituted or unsubstituted primary or secondary alkyl group having 1 to 12 carbon atoms;
Alkyl group, alkoxy group having 1 to 12 carbon atoms, amino group,
A substituted amino group having 1 to 12 carbon atoms,
For example, R ^Two The same as those listed for
Can be mentioned. R ⁹ Particularly preferred as
Substituted or unsubstituted primary or secondary having 1 to 12 carbon atoms
A lower alkyl group. The active methyl represented by X described above
Among the len groups, it shows a particularly preferable effect in the present invention.
The R ^Two COCH _Two COO-, NCCH _Two COO-, R ^Two COCH _Two CO-, NC-CH
_Two CO-. The shell in the latex of the present invention is described below.
Having an active methylene group that gives a repeating unit constituting
Specific examples of monomers will be given, but the present invention is not limited to these.
It is not done. M-1 2-acetoacetoxyethyl methacrylate M-2 2-acetoacetoxyethyl acrylate M-3 2-acetoacetoxypropyl methacrylate M-4 2-acetoacetoxypropyl acrylate M-5 2-acetoacetamidoethyl methacrylate M- 6 2-acetoacetamidoethyl acrylate M-7 2-cyanoacetoxyethyl methacrylate M-8 2-cyanoacetoxyethyl acrylate M-9 N- (2-cyanoacetoxyethyl) acryl
Amide M-10 2-propionylacetoxyethyl acrylate
M-11N- (2-propionylacetoxyethyl) meth
Tacrylamide M-12 N-4- (acetoacetoxybenzyl) phenyl
Racrylamide M-13 Ethyl acryloyl acetate M-14 Acryloyl methyl acetate M-15 N-methacryloyloxymethyl acetoacetoacetate
Amide M-16 Ethyl methacryloylacetoacetate M-17 N-allyl cyanoacetamide M-18 2-cyanoacetylethyl acrylate M-19 N- (2-methacryloyloxymethyl) cia
Noacetamide M-20 p- (2-acetoacetyl) ethylstyrene M-21 4-acetoacetyl-1-methacryloyl pipe
Razine M-22 ethyl-α-acetoacetoxy methacrylate M-23 N-butyl-N-acryloyloxyethyl ethyl
Cetoacetamide M-24 p- (2-acetoacetoxy) ethylstyrene In the polymer constituting the shell of the present invention,
Is an ethylenically unsaturated monomer containing an active methylene group as described above.
Other ethylenically unsaturated monomers are copolymerized
May be. Specific examples of such monomers include
Lylic acid or a salt thereof, an alkyl acrylate (for example,
Methyl acrylate, ethyl acrylate, n-butyl
Acrylate, n-hexyl acrylate, benzyl
Acrylate, 2-ethylhexyl acrylate, n-do
Decyl acrylate, t-butyl acrylate, phenyl
Acrylate, 2-naphthyl acrylate, etc.), meta
Crylic acid or its salt, alkyl methacrylate (eg
For example, methyl methacrylate, ethyl methacrylate,
2-hydroxyethyl methacrylate, benzyl methacrylate
Acrylate, 2-hydroxypropyl methacrylate,
Phenyl methacrylate, cresyl methacrylate, 4-
Chlorobenzyl methacrylate, ethylene glycol di
Methacrylate, n-butyl methacrylate, n-hex
Sil methacrylate, 2-ethylhexyl methacrylate
, N-dodecyl methacrylate), vinyl esters (for example, vinyl acetate,
Vinyl benzoate, pivaloyloxyethylene, etc.)
Lilamides (eg, acrylamide, methylacrylic
Luamide, ethyl acrylamide, propyl acrylia
Amide, butylacrylamide, tert-butylacrylia
Amide, cyclohexylacrylamide, benzylacrylic
Luamide, hydroxymethylacrylamide, methoxy
Ethyl acrylamide, dimethylaminoethyl acryl
Amide, phenylacrylamide, dimethylacrylia
Amide, diethylacrylamide, β-cyanoethylac
Lilamide, diacetone acrylamide, 2-acrylic
Amide-2-methylpropanesulfonic acid, etc.), methacrylic acid
Luamides (for example, methacrylamide, methylmethac
Lilamide, ethyl methacrylamide, propyl methac
Lylamide, butylmethacrylamide, tert-butylmeth
Tacrylamide, cyclohexylmethacrylamide,
Benzyl methacrylamide, hydroxymethyl methacryl
Amide, methoxyethyl methacrylamide, dimethyla
Minoethyl methacrylamide, phenyl methacrylamide
Dimethyl methacrylamide, diethyl methacrylua
Amides, β-cyanoethyl methacrylamide, etc.), styrenes (eg, styrene, methyls
Tylene, dimethylstyrene, trimethylstyrene, ethyl
Styrene, isopropyl styrene, chlorostyrene,
Methoxystyrene, acetoxystyrene, chlorstyrene
, Dichlorostyrene, bromostyrene, vinyl benzoate
Acid methyl ester), divinylbenzene, acrylonitrile
Tolyl, methacrylonitrile, N-vinyl pyrrolide
, N-vinyloxazolidone, vinylidene chloride,
Nyl vinyl ketone, itaconic acid, maleic acid, itacone
Monoalkyl acid (e.g., monomethyl itaconate,
Monoethyl conate, etc.), monoalkyl maleate (eg
For example, monomethyl maleate, monoethyl maleate
Etc.) and citraconic acid. The core / shell polymer latex of the present invention
Has an active methylene group in the shell polymer
The proportion of monomer units used depends on performance requirements.
In the range of 0.1 to 100% by weight
Can be used. However, models with active methylene groups
Increasing the copolymerization amount of the monomer unit increases the various effects described above.
Although the fruit grows, the effect saturates above a certain amount.
0.1 to 60% by weight, especially
Preferably it is 1 to 40% by weight. The core of the present invention
/ Shell polymer in latex / shell polymer latex
The amount ratio of the gel polymer can be arbitrarily changed.
A / shell weight ratio 10/90 to 95/5, preferred
20/80 to 95/5, particularly preferably 30/80
70 to 90/10. Active with too little core
The concentration effect of the methylene monomer on the shell part is reduced,
Too few shells make it difficult to form a clear core / shell structure
It becomes difficult. Also, particles of core / shell polymer latex
The diameter of the core is 1.0 μm or less similarly to the core polymer particles, and
It is preferably 0.7 μm or less, particularly preferably 0.5 μm or less.
is there. And, it is preferable that the thickness is 0.0001 μm or more.
New Core / shell latex formation technology in emulsion polymerization
As is well known in the art,
The polarity of the shell polymer is so close that it is compatible
If the combination does not form the desired core / shell structure
In some cases. However, it is used for the core in the present invention.
The conjugated diene monomer is extremely low in polarity, as described above.
Of all available monomers and the effective core / shell
It can be said that a well structure can be formed. In addition, near polarity
Even when a new monomer is used for the shell, the core
The three-dimensional cross-linking by
It can be a core / shell particle. Core of the present invention /
In shell polymer latex, core polymer or
Or shell polymer, or both,
It may be. In this case, the molecular weight of the resulting polymer is infinite
Is big. The amount of the polymer of the present invention
Although the molecular weight varies depending on the type of monomer and the synthesis conditions, 50
Between 2 and 2 million, depending on the purpose
It is also possible to adjust the molecular weight with a chain transfer agent, etc.
You. Further, it is well known in the radical polymerization technical field.
As described, the core / shell polymer latex of the present invention is
Shell polymer copolymerizes conjugated diene monomer
A portion of the core polymer undergoes a graft polymerization reaction.
And may form a graft polymer. In this case,
As a result, the latex polymer as a whole is
Remer, the above graft polymer, not grafted
The result is a mixture of three shell polymers. Hereinafter, the present invention
Preferred examples of the core / shell latex are shown below.
The present invention is not limited to these. Each of the following la
The structure of the Tex compound is based on the core polymer structure (copolymer
Nomer and composition ratio), the structure of the shell polymer (copolymer
Nomer and composition ratio) and core / shell ratio.
And the copolymer composition ratio and core / shell
All well ratios were expressed as weight percentage ratios. P-1 to 12 core = styrene / butadiene (37/63) P-1 shell = styrene / M-1 (98/2) core / shell = 50/50 P-2 shell = styrene / M-1 (96/4) Core / Shell = 50/50 P-3 Shell = Styrene / M-1 (92/8) Core / Shell = 50/50 P-4 Shell = Styrene / M-1 (84/16) Core / Shell = 50/50 P-5 shell = styrene / M-1 (68/32) core / shell = 50/50 P-6 shell = styrene / M-1 (84/16) core / shell = 67/33 P-7 shell = styrene / M-1 (84/16) core / shell = 75/25 P-8 shell = n-butyl acrylate / M-1 (96/4) core / shell = 50/50 P-9 shell = n-butyl acrylate / M-1 (92/8) core / shell = 50/50 P-10 shell = n-butyl acrylate / M-1 (84/16) core / shell = 50/50 P-11 shell = methyl acrylate / M-7 (84/16) core / shell = 50/50 P-12 shell = Tylene / methyl acrylate / M-3 (21/63/16) core / shell = 50/50 P-13-16 core = styrene / butadiene copolymer (23/77) P-13 shell = styrene / M-1 (92/8) core / shell = 50/50 P-14 shell = styrene / M-2 (84/16) core / shell = 50/50 P-15 shell = n-butyl acrylate / M-1 (84/16) core / shell = 50/50 P-16 shell = n-butyl acrylate / M-8 / acrylic acid (80/16
/ 4) core / shell = 50/50 P-17-22 core = polybutadiene homopolymer (100) P-17 shell = styrene / M-1 (84/16) core / shell = 50/50 P -18 shell = ethyl acrylate / M-7 / methacrylic acid (65/15
/ 20) core / shell = 85/15 P-19 shell = n-butyl acrylate / M-1 (84/16) core / shell = 50/50 P-20 shell = n-butyl acrylate / M-2 (84 / 16) core / shell = 50/50 P-21 shell = 2-ethylhexyl acrylate / M-24 (84/16) core / shell = 50/50 P-22 shell = n-butyl acrylate / M-18 (84 / 16) core / shell = 50/50 P-23-25 core = polyisoprene homopolymer (100) P-23 shell = styrene / acrylonitrile / M-1 (63/21/16) core / shell = 90/10 P-24 shell = methyl methacrylate / ethyl acrylate / M
-2 / 2-acrylamide-2-methylpropanesulfonic acid
Thorium (15/65/15/5) core / shell = 75/25 P-25 shell = styrene / M-1 (84/16) core / shell = 20/80 P-26,27 core = styrene / Butadiene (49/51) P-26 shell = styrene / butyl acrylate / M-1 (25/60/15) core / shell = 50/50 P-27 shell = M-1 (100) core / shell = 90 / 10 P-27 Shell = Lauryl methacrylate / Butyl acrylate
/ M-7 (30/55/15) core / shell = 40/60 P-29 core = styrene / butadiene (63/37) shell = butyl acrylate / 2-hydroxyethyl meta
Acrylate / M-2 (65/15/20) core / shell = 50/50 P-30 core = acrylonitrile / butadiene (50/50) shell = butyl acrylate / 2-butyl methacrylate
/ M-1 (40/40/20) core / shell = 50/50 P-31 core = acrylonitrile / styrene / butadiene (25/2
5/50) Shell = butyl acrylate / M-1 (92/8) Core / shell = 50/50 P-32 Core = ethyl acrylate / butadiene (40/60) Shell = styrene / divinylbenzene / M-1 ( 79/5/16) Core / shell = 50/50 P-33 Core = Ethyl acrylate / styrene / butadiene (40/30
/ 30) shell = ethylhexyl acrylate / M-7 (84/16) core / shell = 50/50 The core / shell polymer latex of the present invention
Is an aqueous dispersion of a core polymer obtained by emulsion polymerization.
To form a shell for the core latex polymer
Emulsion polymerization is carried out while adding or dropping the nomer at once.
Can be easily obtained. Emulsion polymerization is preferred
Preferably, use at least one emulsifier to mix with water or water
Water-miscible organic solvents (eg methanol, ethanol
Emulsify the monomer in a mixed solvent of
Generally, from 30 ° C. to about 10 ° C. using a radical polymerization initiator.
At a temperature of 0 ° C, preferably 40 ° C to about 90 ° C.
Can be. The amount of organic solvent miscible with water is
The product ratio is 0 to 100%, preferably 0 to 50%. The polymerization reaction is usually carried out with respect to the monomer to be polymerized.
0.05 to 5% by weight of a radical polymerization initiator and optionally
And 0.1 to 10% by weight of an emulsifier. polymerization
Initiators include azobis compounds, peroxides,
For example, hydroperoxide, redox catalyst, etc.
Potassium sulfate, ammonium persulfate, tert-butyl par
Octoate, benzoyl peroxide, isopropyl
Lucanate, 2,4-dichlorobenzylperoxa
Ide, methyl ethyl ketone peroxide, cumene high
Dropper oxide, dicumyl peroxide, 2,
2'-azobisisobutyrate, 2-2'-azobis
(2-amidinopropane) hydrochloride, persulfuric acid
There are combinations of potassium and sodium bisulfite. milk
As an agent, anionic, cationic, amphoteric, nonionic
Besides water-soluble surfactants, there are water-soluble polymers and the like. example
Sodium laurate, sodium dodecyl sulfate, 1
-Octoxycarbonylmethyl-1-octoxycarbo
Sodium nylmethanesulfonate, laurylnaphthalene
Sodium sulfonate, laurylbenzene sulfonate
Thorium, sodium lauryl phosphate, cetyltrimethyl
Luammonium chloride, dodecyl trimethylenean
Monium chloride, N-2-ethylhexylpyridini
Um chloride, polyoxyethylene nonylphenyl ether
-Tel, polyoxyethylene sorbitan lauryl ester
Sodium, dodecyl-diphenyl ether disulfonic acid
, Sodium 2-tetradecene-1-sulfonate,
Sodium 3-hydroxytetradecane-1-sulfonate
, Gelatin, PVA, etc.
Emulsifiers, water-soluble polymers, etc.
Nonionic or nonionic surfactant, water-soluble poly
Mer are particularly preferred. In the emulsion polymerization, the addition of the monomer
Avoids heat generation associated with
It is preferable to add while dropping from the viewpoint of formation. Ma
In addition, the above initiator, in the presence of an emulsifier, by emulsion polymerization
After forming the core latex particles, the shell monomer is
When mixing, an emulsifier may be further added or added.
Alternatively, the polymerization may be carried out without performing the above. Addition of emulsifier depends on the polymer
-Often required from the viewpoint of latex stability
However, if an excess emulsifier is present,
Particles consisting only of limers may be by-produced.
Therefore, the amount of emulsifier added after core polymer formation
To 0.001 to 5% by weight of the particles
Or it is preferable not to add them at all. Effective core / shell
Shell to form a latex with
Can polymerize core particles during addition of forming monomer
It is preferable that the polymerization rate is 90% or more,
Preferably at least 95%, particularly preferably substantially 100
%. The aforementioned polymer latex / gelatin composite
Improve film strength in coatings, paint and adhesive latex
In improving various properties, the active methylene unit
Functions as a functional group. Therefore, it exists on the latex surface.
The amount of active methylene units is an important factor in performance. Book
The core / shell latex of the invention is essentially an active methylene
Concentrate units on latex surface where needed
Is useful in that it can be
Regarding the improvement of the film strength in the wet state of the film,
A surprising improvement that cannot be predicted from surface concentration
Show. The core / shell latex particles of the present invention include:
It can be obtained in the form of an aqueous dispersion by the above emulsion polymerization method.
Fine particles while maintaining the core / shell structure
Can be a body. As such a powdering method
Are freeze-dried, coagulation and filtration using strong acids or salts
Flocculation / filtration by repeated freezing and thawing methods
A known method such as an excess method can be used. Perform the following
The present invention will be described in detail by way of examples. Example 1 Core = polybutadiene (homopolymer), shell = styrene
/ 2-acetoacetoxyethyl methacrylate (84
/ 16) core / shell latex (core / shell ratio =
50/50) (Synthesis of Exemplified Compound P-17) 1-liter three-necked flask equipped with a stirrer and a reflux condenser
0.28 g of sodium bisulfite, sodium bicarbonate
3.52 g of a 1 mol / l solution of lithium, 454 of distilled water
g, stirred and dissolved, then polybutadiene latex
(Particle size: 112 nm, solid content: 34.3% by weight: Zeon Corporation)
(Product name: LX-111J) 294.1 g of nitrogen gas
The mixture was heated and stirred at 65 ° C. under flowing water. 0.32 g of potassium persulfate
After adding what was dissolved in 20 g of distilled water, styrene 8
4.0 g, 2-acetoacetoxyethyl methacrylate 1
6.0 g of the mixed solution and 0.16 g of potassium persulfate in distilled water 5
Dropping is completed in 1.5 hours for each of the solutions dissolved in 0 g
Was started at a constant speed as described above. After dropping, heat for 1 hour
After stirring, 0.16 g of potassium persulfate was added to 2 parts of distilled water.
Add the solution dissolved in 0 g and continue heating and stirring for 3 hours.
Was. Cool to room temperature, filter and filter
931.4 g of solid latex (solid content 21.2%, solid
Ratio 98.3%, average particle size 138 nm: particle size is Coulter
Submicron analyzer (measured with Nikkaki)).
Also, a part (100 g) of the obtained latex
And freeze-dried to obtain the core / shell fine particle powder of the present invention.
20.2 g were obtained. Example 2 Core = polybutadiene (homopolymer), shell = n-butyl
Tyl acrylate / 2-acetoacetoxyethyl methacrylate
Relate (84/16) core / shell latex
A / shell ratio = 50/50) (Example compound P-1)
Synthesis of 9) 1-liter three-necked flask equipped with a stirrer and reflux condenser
0.28 g of sodium bisulfite, sodium bicarbonate
3.52 g of a 1 mol / l solution of lithium, 454 of distilled water
g, stirred and dissolved, then polybutadiene latex
(Particle size: 112 nm, solid content: 34.3% by weight: Zeon Corporation)
(Product name: LX-111J) 294.1 g of nitrogen gas
The mixture was heated and stirred at 65 ° C. under flowing water. 0.32 g of potassium persulfate
After adding what was dissolved in 20 g of distilled water, n-butyl was added.
84.0 g of acrylate, 2-acetoacetoxyethyl
Mixture of 16.0 g of acrylate and 0.1 of potassium persulfate
A solution prepared by dissolving 6 g in 50 g of distilled water in 1.5 hours
The dropping was started at a constant speed so that the dropping was completed. Drip end
After heating and stirring for 1 hour, potassium persulfate 0.1
A solution prepared by dissolving 6 g in 20 g of distilled water was added, and further 3 hours
Heating and stirring were continued. After cooling to room temperature and filtering, the desired core / shell
931.0 g of solid latex (solid content 21.0%, solid fraction yield
97.3%, particle diameter 145 nm). Example 1 and
Figure 2 shows an electron micrograph of the polymer latex obtained in Step 2.
1 and 2 (FIG. 1 shows an example of polymer P-17, FIG.
Represents an exemplary polymer P-19). Photo magnification is 10
It is 0000 times, 1cm on the photo is equivalent to 0.1μm
You. Contrast of latex shading is butadiene
Staining of double bonds remaining in polymer (with osmium oxide
Black part is the core polymer, white
The part corresponds to the shell polymer. According to FIG.
In Tex, the conjugated diene polymer core is
Make sure that the shell polymer containing the
That the target core / shell polymer is
And another consisting only of the polymer forming the shell part.
It is clear that no particles are present. Embodiment 3 The above-mentioned P-phase was prepared in basically the same manner as in Embodiments 1 and 2.
Synthesis of other core / shell latex described in 1-33
went. Of these, some core / shell latex
About the particle diameter of the original core latex, the core
Theoretical Core / Sheller Predicted from the Weight / Shell Ratio
Tex particle size, core / shell latex particles obtained
Table 1 shows the measurement results of the diameters. [Table 1] Particle size (nm) Core / shell ratio Core polymer Core / shell Core / shell polymer (weight ratio) (actual measurement) (actual measurement) (calculated value) ─────────────────────── ──────────── P-2 50/50 136 173 171 P-3 50/50 136 168 171 P-4 50/50 136 170 171 P-6 67/33 136 156 150 P- 7 75/25 136 150 146 P-12 50/50 136 168 171 P-17 50/50 112 138 141 P-19 50/50 112 165 141 P-26 50/50 173 211 218 P-29 50/50 197 239 248 ─────────────────────────────────── Note) Calculation method is the specific gravity of each core / shell Was assumed to be the same and calculated as a simple volume increment from the core / shell weight ratio. Therefore, if there is a difference in specific gravity, there may be a slight deviation from the theoretical value. From the results shown in Table 1, the latex obtained by the present invention was obtained.
Cans from core latex to core / shell latex
In the process, the particle size should increase almost to the calculated value.
And from the core latex or shell po
There are almost no particles consisting only of rimer and
Core / shell latex with low agglomeration in process
It is clear that the structure is adopted. Example 4 Gelatin was added to a 6% by weight gelatin solution dissolved at 40 ° C.
50 or 75% by weight polymer content based on solids
The polymer latex of the present invention shown in Table 2 is
Then, as a hardening agent, 1,2-bis (vinyl
Sulfonylacetamide) ethane to 100 g of gelatin
12mmole, dodecyl benzene sulf
1 g of sodium phonate per liter of gelatin solution
As well as polystyrene foam as a thickener.
Sodium sulfonate was added to the gelatin solution to a viscosity of 30 cp.
And a coating solution was prepared. Apply this coating solution to the undercoat layer
Coated polyethylene terephthalate support (thickness
100 μm) and the amount of gelatin applied was 5 g / m ^Two become
And dried. These samples were prepared at 25 ° C. and 55% R
After storing for 1 week under the conditions of H,
The wet film strength was evaluated. [Evaluation Method of Wet Film Strength]
After immersion in distilled water at ℃ for 2 minutes, sapphire with a radius of 0.3 mm
The needle is pressed against the sample membrane surface and moved at a speed of 10 mm / sec.
While the needle load is continuously increased while the membrane breaks
Was determined (g). Table 2 shows the results. [Table 2] Table 2 ───────────────────────────────── Addition amount Active wet polymer in polymer (wt% vs. methylene monomer species and film strength Remarks Gelatin content (wt% vs. polymer) (g) ─────────────────────────── {P-2 50 M-1 2120} P-3 50 M-14 4155 of the present invention {P-4 50 M-18 220} P-4 75 M-18 210 210 P-6 50 M-1 5.3 ２０５ 205 〃 P-750 M-14 170 〃 P-10 50 M-18 170 〃 P-10 75 M-18 155 〃 P-12 50 M-38 175 〃 P -16 50 M-8 8 170 〃 P-17 50 M-18 210 〃 P-20 50 M-2 195 〃 P-22 50 M-18 88 180 〃 P-23 50 M-1 1.6 135 〃 P-28 50 M-7 9200 〃 P-30 50 M-1 10 185 〃 P-34 50 Yellow cap 10 115 〃 Color monomer A-1 50-0 80 Comparative example A -250-078 〃 A-350 M-1 490 A-4 50 M-18 120 〃 A-5 50 M-1 16 145 〃 A-575 M-1 16 128 〃 A-6 50 M-1 35 155 〃 A-750 M-18 125 Ａ A-850 M-1 110 130 Ａ A-950 Yellow cap 18 110 〃 Color monomer A-10 50 Yellow cap 10 100 ラ ー Color monomer added No 0--180 〃 The effect of the core / shell latex of the present invention To prove
Latex compound of the comparative example performed for, and of the present invention
Compound P-34 was synthesized as follows. Comparative Compound A-1 Polybutyl acryle
Latex comparative compound A-2 poly (styrene / butadiene (3
7/63) Copolymer latex Comparative compounds A-3 to 8 Core / shell structure according to JP-B-45-5819.
The following (single-layer type) latex having no compound was synthesized. A-3: butyl acrylate / 2-acetoacetoxyethyl methacrylate (M-1) (96/4: weight ratio) A-4: butyl acrylate / M-1 (92/8) A-5: butyl acrylate / M- 1 (84/16) A-6: Butyl acrylate / M-1 (65/35) A-7: Styrene / butadiene / M-1 (30/62/8) A-8: Butyl acrylate / M-1 / Acrylic acid (75/15/10) According to the description in JP-A-58-42044, the following core / shell
To synthesize a yellow polymer coupler latex
Was. Comparative compounds A-9, 10 Core: butyl acrylate shell: A-9: core / shell = 9.1 / 90.9 A-10: core / shell = 50/50 Compound P-34 of the present invention Core: styrene / butadiene (37/63) copolymer
Body shell: Core / shell = 50/50 From the results in Table 2, it was found that the shell part of the present invention was active.
Polymers with methylene groups are the same active methylene monomer
-Compared to non-core / shell type polymer by content comparison
Regardless of the amount of latex added, the level of film strength
Is high, and from the comparison between P-34 and A-10,
By including conjugated diene monomers, the same core / shell
Higher latex strength can be obtained
I understand. From these results, the polymer latex of the present invention was
The core has a clear core / shell structure
And the usefulness of the polymer latex of the present invention
Is.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an electron micrograph of a polymer P-17 of the present invention. FIG. 2 is an electron micrograph of a polymer P-19 of the present invention.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-59-217701 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 279/00-279/02

Claims (1)

(57) [Claims] 1. Repetition derived from a conjugated diene monomer
A core comprising a polymer having at least one unit
Ethylenically unsaturated monomer having an active methylene group
Shell comprising a polymer having repeating units derived from
And fine particles having a heterogeneous structure.
A latex-like polymer,The weight ratio of each polymer of the core and the shell is 20/80 to 95.
/ 5, and an active methylene group.
The thylene unsaturated monomer is represented by the following general formula (I)
A fine particle having a heterophasic structure, characterized by being a monomer
Latex polymer composed of particles. General formula (I) CH _Two = C (R ¹ ) -LX Where R ¹ Is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or
Represents a halogen atom, L represents a single bond or a divalent linking group
Represents X is R ^Two COCH _Two COO-, NC-CH _Two COO-, R ^Two COCH _Two CO-
, NC-CH _Two CO- (R ^Two Is substituted or unsubstituted having 1 to 12 carbon atoms
A substituted alkyl group, substituted or unsubstituted having 6 to 20 carbon atoms
Aryl group or aryloxy group, having 1 to 12 carbon atoms
Alkoxy group, amino group, substituted amino having 1 to 12 carbon atoms
Represents a group), R ⁹ -CO-CH _Two CON (R ⁶ )-(R ⁶ Is hydrogen atom, carbon
Represents a substituted or unsubstituted alkyl group of Formulas 1 to 6, ⁹
Is a substituted or unsubstituted primary or secondary having 1 to 12 carbon atoms.
Alkyl group, alkoxy group having 1 to 12 carbon atoms, amino
A substituted amino group having 1 to 12 carbon atoms)
And when L is not a single bond, L is X
Alkylene, aralkylene or arylene
In the form of