JPS58196221A - Nonaqueous type resin dispersion and preparation thereof - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a nonaqueous resin dispersion useful for electrophotographic liquid developers, inks, adhesives, etc., and a method for producing the same.

Various proposals have been made regarding non-aqueous resin dispersions used in electrophotographic liquid i-image agents, inks, adhesives, etc., and methods for producing the same. For example, U.S. Patent No. 4,087,
No. 393 specifies that in a non-aqueous solvent composed of aliphatic hydrocarbons a) a seven-mer compound (after polymerization) represented by the general formula % formula % (RFiB or -0H, n is an integer of 8 to 20); a step of copolymerizing a monomer that can be solvated in a non-aqueous solvent with a monomer having a glycidyl group such as glycidyl acrylate or glycidyl methacrylate; b) copolymerizing the resulting copolymer with calzexyl such as acrylic acid, methacrylic acid, itaconic acid, or maleic acid; esterifying with a monomer having a group; and ) Styrene, methyl methacrylate,
A method for producing a non-aqueous resin dispersion by continuously performing a step of grafting a vinyl monomer such as vinyl acetate (a monomer that becomes insoluble in a non-aqueous solvent after polymerization) is disclosed.

However, the dispersion used in this method has a large resin particle size and is non-uniform, resulting in poor dispersion stability, resulting in sedimentation and gelation over time.2)
It has disadvantages such as poor dispersion stability for pigments, pigment aggregation over time when used as a paint, and inability to form a coating film with secondary flexibility and water resistance. There is.

The first object of the present invention is to provide a non-aqueous resin dispersion in which sedimentation and gelation of the resin are prevented by making the particle size of the resin minute and uniform.

A second object of the present invention is to provide a non-aqueous resin dispersion that can prevent pigment agglomeration and form a flexible and water-resistant coating film by improving dispersion stability for pigments.

A third object of the present invention is to provide a non-aqueous resin dispersion containing a resin that is hot meltable and thus particularly useful as a hot melt adhesive.

The non-aqueous resin dispersion of the present invention and its manufacturing method are as follows.

That is, the non-aqueous resin dispersion of the present invention contains an olefinic copolymer having a hydroxyl group, unsaturated carminic acid or its anhydride, and the general formula I R in a non-aqueous solvent comprising an aliphatic hydrocarbon.

CH, C-2 [However, R1 is -H or -C) Is%z is -COOCnH
1m+ or -QCnH*n+t (n is an integer from 6 to 20). ] It is made by dispersing a resin containing the acrylic monomer 1- as a constituent component.

In addition, there are two methods for producing the non-aqueous resin dispersion of the present invention.The first method is to produce a non-aqueous resin dispersion in which a) an olefinic copolymer having a hydroxyl group and an unsaturated carminic acid or its anhydride, and the subsequent step 1b) of grafting the acrylic monomer of the general formula I to the obtained tiger esterified product.The second method is aliphatic carbonization. A step of copolymerizing a) unsaturated carminic acid or its anhydride with the acrylic monomer of the general formula (1) in a non-aqueous solvent consisting of hydrogen, followed by b) the resulting copolymer having t-carminic acid. The process involves esterifying the polymer and a copolymer having hydroxyl groups.

The olefin copolymer having a hydroxyl group used in the present invention is a binary copolymer of an olefin and an olefin alcohol as shown in the following general formula, or a binary copolymer of these monomers and vinyl acetate, vinyl chloride, (methane acrylic acid) Alternatively, it refers to a copolymer with a polymerizable monomer such as (meth)acrylic ester.

General formula] R1 [However, R8 is -OH or Cm)i! mOH(m #11
~20 integers), j is an integer from 1 to 3, and x and y represent repeating units. ] Here, the olefins are ethylene, l-butene, and t
Examples of the olefin alcohol include allyl alcohol, crotyl alcohol, allyl carbinol, citronellol, and phytol.

Among such olefinic copolymers having a Z-dihydroxyl group, specific examples of unsaturated cardanic acid or its anhydride in the binary copolymer of general formula 1 include acrylic acid, methacrylic acid, 7-maric acid, itaconic acid, crotonic acid, maleic acid,
Examples include maleic anhydride and those having the following structural formula.

■ 1, CM, -C-COOCH, -CH, -00
0-CM, -CH, -CoolCl.

2, CH, -C-COOC)I, -〇H, -0
0C-CM, -CH, -COOH3, CI(, -C-
COOCH, -CH, -00C-CH-CH-Cool
CH.

4, CH, -C-COOCH, -CM, -00C
-CM-CH-Coo17, CHI-C-CO
OCHI-CHI-000-CHI-C-Cool
Compound A Structure Formula % Formula % Specific examples of the acrylic thread member of general formula I include lauryl methacrylate, lauryl acrylate, stearyl methacrylate, stearyl acrylate, dodecyl methacrylate, dodecyl acrylate, cetyl methacrylate, cetyl acrylate, etc. .

In addition, aliphatic hydrocarbons used as non-aqueous solvents include n-hexane, inooctane, isododecane, and n-nonane.
There are H, L*M and Shell Sol 71 manufactured by Shell Oil.

To carry out the method of the present invention, in the first method, an olefinic copolymer and an unsaturated CalIyiI2 or anhydride thereof are mixed in an aliphatic hydrocarbon with an esterification catalyst such as am or lauryl dimethylamine. The reaction is carried out at a temperature of 50 to 100°C in the presence of. This causes esterification,
Grafted active sites are formed on the copolymer. ζHere, the olefin copolymer is a component that contributes to the fixing properties and hot melt properties of the resulting resin, while the unsaturated carbon copolymer
The anhydride is a component that forms the graft active sites of this resin.

Next, the esterified product obtained by ζ and the Acryph monomer of the general formula let As a result, the monomer of general formula 1 is grafted onto the reesterified product. Here, the esterified product is a polymer or a polyolefin component of an alkyl ester having 1 to 6 carbon atoms of acrylic acid or methacrylic acid that is insoluble in the aliphatic hydrocarbon medium, while the acrylic yarn thread is formed after polymerization. A component that solvates in a solvent. In the first method, the amounts of the unsaturated carboxylic acid or its anhydride and the acrylic monomer of the general formula (2) are respectively based on 1 part by weight of the olefin copolymer, and J) 0.001 to 0.s parts by weight. , 0.0
Approximately 01 to OS weight parts are additional teeth.

Next, regarding Shinji's method, you can follow the same method as the first method except for changing the material used.

The non-aqueous resin dispersion obtained in the above manner has extremely good dispersibility, hot melting properties, and fixing properties because the resin is not partially dissolved in the solvent and is partially solvated. Because of its excellent properties, it can be effectively used in hot melt adhesives, electrophotographic liquid developers, and inks.

Examples of the present invention are shown below. Note that all parts are parts by weight.

Example 1 200% of isooctane was placed in a four-roof flask equipped with a thermometer, a stirrer, and a condenser, and heated to 90°C on an oil path. 1 part and concentrated sulfur @ part S were added, and the esterification reaction was carried out at the above temperature for 5 hours. Next, 100 parts of stearyl methacrylate and 5 parts of penzoylno-9-oxide were added to the mixture, and a graft copolymerization reaction was carried out at 90°C for S hours to achieve a polymerization rate of 90.8- and a resin particle size of o, s-.
1. A non-aqueous resin dispersion having an OJm and a liquid viscosity of 80 cp (20°C) was obtained.

Example 2 The same four flasks as in Example 1 were heated at 90°C on an oil path.
After heating to ℃, lauryl methacrylate) 10
A compound w3os having the formula AIG and 1 part of benzoyl peroxide were added, and a copolymerization reaction was carried out at 90° C. for 3 hours. Next, in this, 1 part of hydroquinone, 50 parts of an olefin copolymer of KH2, and 0.002 parts of dobusylaquine were added.
The esterification reaction was carried out at 90°C for 5 hours, and then Iso/''-0200JI was added and stirred.Thus, the polymerization rate *sol, the resin particle size 0.3 to o, sμ, and the liquid viscosity 5
A non-aqueous resin dispersion liquid of oap (110° C.) was obtained.

Example 3 300 parts of IK n-hexane were taken and heated to 90°C, and then 1 part of stearyl methacrylate (1 part of methacrylic acid, 5 ISJj [lauroyl peroxide ss] was added). , a copolymerization reaction was carried out at 80°C for 5 hours. 70.1 parts of hydroquino, 0.001 part of lauryl dimethylamine, and 30% of ACI olefin copolymer were added, and the mixture was esterified at 80°C for 10 hours. The resin particle size was 0.2~ at a polymerization rate of 98.s.
A resin dispersion having a liquid viscosity of 0.8μ and a liquid viscosity of 260 cp (20°C) was obtained.

Example 4 The method of Example 1 was repeated except that AAI was used as the olefin copolymer, and the resin particle size was 0.2 to 0 at a polymerization rate of OSg.
, sμ, and a liquid viscosity of 30 ep (20°C) were obtained.

Example 5 The method of Example 2 was repeated using 7-maric acid instead of the compound having the structural formula Ale, and the other conditions were repeated to obtain a polymerization rate of 93 J- and a resin particle size of 0.
A well water-based resin dispersion having a diameter of 5 to 10 μm and a liquid viscosity of 60 cp (20° C.) was obtained.

*Processing f116-12 A non-aqueous resin dispersion was produced in the same manner as in Example 1, except that the solvent, olefin copolymer, and unsaturated carmine or its anhydride were those listed in Table IK. The polymerization rates and properties of these dispersions are shown in Table 2.

(The following is a blank space) Table 2 The nonaqueous resin dispersions obtained in Examples 1 to 12 above were stored at room temperature for 180 days, but no gelation or aggregation was observed.

Claims (1)

[Claims] 1. An on-2-yne copolymer having a hydroxyl group, unsaturated calmic acid or its anhydride, and the general formula I 1 CM, -c-2 in a non-aqueous solvent consisting of an aliphatic hydrocarbon. [However, R1 is -H or -CH5, z is -COOCmH1
m+1 or -0CnH snow n+t (1 is an integer from 6 to 2 G). ] A non-aqueous resin dispersion prepared by dispersing a resin containing an acrylic monomer shown as a constituent component. 2. A step of esterifying a) an olefinic copolymer having a hydroxyl group and an unsaturated carboxylic acid or its anhydride in a non-aqueous solvent consisting of an aliphatic hydrocarbon, and subsequently b) the resulting next ester General formula I CH鵞-C-Z [However, R1 is -H or -cmj, z is -COOCmH1
n+ or -〇〇sH1m+1C group is an integer from 6 to 20)
to show. ] A method for producing a non-aqueous resin dispersion, which comprises performing a step of grafting an acrylic monomer as shown in the following. 3. a) Unsaturated carzenic acid or its anhydride in a non-aqueous solvent consisting of an aliphatic hydrocarbon and the general formula I1 CH, C-Z [However, R, Fi-H or -CH, Z is -COOCmH
*A step of copolymerizing m+ or -0CnH1n+t (n is an integer from 6 to 200) with an acrylic monomer,
and a subsequent step of b) esterifying the obtained copolymer having Calzy* and an olefin copolymer having a number of water groups.