JPH0450269A - Vinyl chloride resin-based ink vehicle - Google Patents

Abstract

PURPOSE:To provide the subject vehicle composed of a vinyl. chloride-based resin consisting of a copolymer between vinyl chloride and an N-substituted maleimide and an organic solvent, having a low melting viscosity and excellent in dispersion force for an inorganic pigment and heat seal resistance. CONSTITUTION:An objective vehicle composed of a vinyl chloride-based resin consisting of a copolymer between 50-99wt.% vinyl chloride and 1-50wt.% N- substituted maleimide (preferably N--cyclohexylmaleimide or N-phenylmaleimide) and an organic solvent (e.g. methyl ethyl ketone). In addition, a polymerizable monomer containing one or more groups selected from hydroxyl group, sulfonic acid group, sulfonate group, carboxyl group, phosphoric acid group, quaternary ammonium salt group and amino group is preferably further contained in an amount of 0.05-10wt.% as the above-mentioned copolymer component.

Description

[Detailed description of the invention] (Industrial application field) The present invention relates to vinyl chloride resin based ink vehicles.

(Prior Art) Conventionally, vinyl chloride resin has been dissolved in an organic solvent and used as an ink vehicle, but due to the excellent chemical resistance of vinyl chloride resin, tetrahydrofuran,
Vinyl chloride resins are unsuitable for use as ink vehicles because they are soluble only in specific solvents such as cyclohexane and dioxane, and even when dissolved, the viscosity of the solution becomes high.

In order to solve the above-mentioned drawbacks, vinyl chloride has been copolymerized with other monomers. As this copolymer, for example, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-vinyl alcohol copolymer, etc. are known. Furthermore, Japanese Patent Publication No. 52-50204 proposes a vinyl chloride copolymer consisting of vinyl chloride and 2-hydroxypropyl acrylate as a binder that can disperse inorganic pigments well. 62-
112217 and JP-A-1-184629 propose vinyl chloride copolymers containing epoxy groups.

However, the above resins had the disadvantage that they could not be dissolved at high concentrations in general purpose solvents. In addition, since the solution viscosity is high when the above resin is dissolved in a general-purpose solvent,
The dispersibility of the inorganic pigment was insufficient. Moreover, when the above resin was used as an ink vehicle, it could not exhibit sufficient performance as an ink vehicle due to its low heat sealing resistance.

(Problems to be Solved by the Invention) The present invention has been made in view of the above drawbacks, and has a low solution viscosity when dissolved in a solvent, excellent dispersibility of inorganic pigments, and excellent heat sealing resistance. The purpose of the present invention is to provide an excellent vinyl chloride resin ink vehicle.

(Means for Solving the Problems) As a result of intensive research to solve the above problems, the present inventors have found that a copolymer of vinyl chloride and N-substituted maleimide is optimal for use as an ink vehicle. I found it. Copolymers of vinyl chloride and N-substituted maleimide are disclosed in Japanese Patent Publication No. 41-9551 and Japanese Patent Publication No. 44-12433.
Although it is a well-known vinyl chloride resin as described in the above publication, it has hitherto been limited to molding applications.

As a result of our research, the present inventors found that a copolymer of vinyl chloride and N-converted maleimide is soluble in general-purpose solvents, the resulting solution has a low viscosity, has excellent dispersibility of inorganic pigments, and is highly resistant. They discovered that it has excellent heat sealability and has outstanding performance as a resin for ink vehicles.

N-substituted maleimide (bl is a compound represented by the following formula) used in the present invention.

In the formula, R is not particularly limited as long as it is an aliphatic group, an alicyclic group, or an aromatic group having 1 to 20 carbon atoms, and is, for example, N-methylmaleimide, N-n-propylmaleimide, N- Isopropylmaleimide, N-n-butylmaleimide, N-tert-butylmaleimide, N-n-hexylmaleimide, N-cyclohexylmaleimide, N-
Phenylmaleimide, N-2-chlorophenylmaleimide, N-2-methylphenylmaleimide, N-2-ethylphenylmaleimide, N-2,6-', ;') lorophenylmaleimide, N-2,6-dimethylphenylmaleimide enylmaleimide, N-benzylmaleimide, N-(2-chlorobenzyl)maleimide, N-(2-methylbenzyl)maleimide, N-naphthylmaleimide, etc., and N-di-chlorohexylmaleimide and N-phenylmaleimide. Suitably used.

The vinyl chloride resin of the present invention is vinyl chloride (al and the above N
-substituted maleimide), but the content of vinyl chloride (a) is small (if the content is low, the copolymer will become hard and the flexibility will decrease, and if it is large, the solubility in organic solvents will decrease). 59 to 99% by weight, and when the content of N-f exchanged maleimide decreases, the solubility in organic solvents and the heat resistance of the copolymer decrease, and the copolymer becomes hard and flexible. is 1 to 50% by weight.

The average degree of polymerization of the copolymer is preferably from 100 to 800 because if it becomes small, the mechanical strength of the ink coating will decrease, and if it becomes large, the solution viscosity when dissolved in an organic solvent becomes too high, making it difficult to use as an ink.

Any method may be used to produce the above-mentioned copolymer; for example, the known suspension polymerization method, emulsion polymerization method, which is usually carried out in the polymerization of vinyl chloride using a radical polymerization initiator,
Examples include solution polymerization method and bulk polymerization method.

The suspension polymerization method is preferably employed because the resulting polymer does not contain impurities and the manufacturing cost is relatively low.

In the above suspension polymerization method, the suspension stabilizer is not particularly limited, and for example, partially saponified polyvinyl alcohol, cellulose derivatives, sodium polyacrylate, etc. are used, and the radical polymerization initiator is not particularly limited. For example, organic peroxides such as hensyl peroxide, dilauroyl peroxide, tert-butylperoxyneodecanoate, and azobis-based compounds such as abbisisobutyronitrile are used.

The N-substituted maleimide may be added all at once into the polymerization vessel before the start of polymerization, or may be added in portions during polymerization, or may be added continuously.

In particular, N whose copolymerizability ratio with vinyl chloride is significantly different
- When using an N-substituted maleimide such as phenylmaleimide, it is better to add the entire amount in portions or continuously during polymerization to obtain a uniform composition, which improves solubility in organic solvents. Therefore, it is preferable. In this case, the N-substituted maleimide is preferably dissolved in an organic solvent such as acetone or methanol, or dispersed in water. Moreover, at this time, a chain transfer agent such as n-dodecylmercaptan or mercaptoethanol may be used as necessary.

The polymerization temperature is generally 30 to 90°C, and the polymerization time is generally 2 to 20 hours.

The organic solvent used in the present invention is not particularly limited as long as it dissolves the above copolymer, and for example,
Examples include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, ethers such as tetrahydrofuran and dioxane, esters such as ethyl acetate and butyl acetate, and nitrogen-containing compounds such as nitrobenzene and N,N-dimethylformamide. These may be used alone or in combination of two or more.

Further, if necessary, a diluting solvent such as toluene or xylene may be used in combination.

The vinyl chloride resin vehicle of the present invention is prepared by dissolving the copolymer in the organic solvent, and the concentration of the copolymer in the solution may be determined as appropriate depending on the purpose.

The second invention of the present invention provides that the above polymer further contains at least one selected from the group consisting of a hydroxyl group, a sulfonic acid group, a sulfonic acid group, a carboxyl group, a phosphoric acid group, a quaternary ammonium base, and an amino group. The contained polymerizable monomer (c1) is copolymerized.

The above polymerizable monomers (c1 are used alone or in combination of two or more.

The polymerizable monomer containing a hydroxyl group is not particularly limited as long as it has a reactive double bond and a hydroxyl group. For example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth) ) acrylate,
3-chloro-2-hydroxypropyl (meth)acrylic
rate, polyethylene glycol mono, expressed by the following formula:
(meth)acrylate (n is an integer from 2 to 9, R1 is hydrogen or methyl group), CH2=CR'-CObeCHz-CHz-0)--H^ Polypropylene glycol mono (meth)acrylate represented by the following formula (n is an integer of 2 to 6, R2 is hydrogen or methyl group), reaction product of (meth)acrylic acid ester such as 2-hydroxyethyl-2-acryloyloxyphthalate and polyhydric alcohol, N-methylol (meth)acrylamide (meth)acrylic acid-based amides such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate are preferably used.

The polymerizable monomer containing a sulfonic acid group or sulfonic acid group is not particularly limited as long as it has a reactive double bond and a sulfonic acid group or a sulfonic acid group (for example, 2- Examples include acrylamide-2-methylpropanesulfonic acid and sodium metaallylsulfonate.

The polymerizable monomer containing a carboxyl group is not particularly limited as long as it has a reactive double bond and a carboxyl group, and examples include acrylic acid, methacrylic acid, and mono(meth)acryloyl succinate. Examples include oxyethyl ester, phthalic acid mono(meth)acryloyloxyethyl ester, maleic acid n-butyl monoester, maleic acid, fumaric acid, etc.
Methacrylic acid, n-butyl maleate monoester and maleic acid are preferably used.

The polymerizable monomer containing a phosphoric acid group is not particularly limited as long as it has a reactive double bond and a phosphoric acid group; for example, acid phosphooxyethyl (meth)
Examples include acrylate, acid phosphoxypropyl (meth)acrylate, and 3-chloro-2-acid phosphoxypropyl (meth)acrylate.

The polymerizable monomer containing the above quaternary ammonium base is
There are no particular limitations as long as it has a reactive double bond and a quaternary ammonium base. 3-
Examples include methacryloylamide-propylammonium chloride.

The polymerizable monomer containing an amino group is not particularly limited as long as it has a reactive double bond and an amino group, and examples thereof include dimethylamino (meth)acrylate, diethylamino (meth)acrylate, N, N
-dimethylaminopropylacrylamide, ter-butylaminoethyl (meth)acrylate, and the like.

The content of the polymerizable monomer (c) should be set to 0.0.
05 to 10% by weight.

The structure of the vinyl chloride resin-based ink vehicle of the present invention is as described above, but it can be copolymerized with vinyl chloride within a range that does not reduce the basic performance as an ink vehicle such as solubility in organic solvents and dispersibility of inorganic pigments. Possible monomers may be copolymerized, and their content is preferably 10 M% or less.

The above monomer is not particularly limited, but
For example, α-olefins such as ethylene and propylene,
Vinyl esters such as vinyl acetate and vinyl propionate, vinyl ethers such as butyl vinyl ether and cetyl vinyl ether, acrylic esters such as methyl acrylate and ethyl acrylate, methacrylic esters such as methyl methacrylate, ethyl methacrylate, and phenyl methacrylate, styrene , aromatic vinyls such as α-methylstyrene, vinyl cyanides such as acrylonitrile and methacrylonitrile, vinyl halides such as vinylidene chloride and vinyl fluoride, unsaturated dicarboxylic acid esters such as dimethyl maleate and dimethyl fumarate. and unsaturated dicarboxylic acid anhydrides such as maleic anhydride.

The vinyl chloride resin ink vehicle of the present invention may optionally contain inorganic pigments such as carbon black, titanium oxide, calcium carbonate, barium sulfate, chrome yellow, cadmium yellow, phthalocyanine blue, phthalocyanine green, and cadmium red, aluminum powder, Metal powders such as bronze powder, coloring agents such as organic pigments and dyes, vegetable oils such as linseed oil and cut oil, mineral oils such as machine oil and spindle oil, coloring agents such as processing oils, dispersants, emulsifiers, and skin coatings. Preventive agents, antifoaming agents, stabilizers, plasticizers, etc. may be added.

In addition, the solubility in organic solvents, the dispersibility of inorganic pigments,
Acrylic resins, alkyd resins, phenolic resins, ketone resins, nitrocellulose,
Other resins may be added, such as cellulosic resins such as ethylcellulose, natural resins such as pine resin, rosin, shellac, giltstone, etc.

(Example) The present invention will be explained in detail below.

The methods for measuring the degree of polymerization, composition, and physical properties of the vinyl chloride copolymer shown in the results as an ink vehicle are as follows.

(1) Degree of polymerization Measured according to flS K672L.

(2) Composition After measuring the chlorine content by the oxygen flask combustion method, use an elemental analyzer (manufactured by Yanagimoto Seisakusho Co., Ltd., model: CHN Coder M).
The component composition was determined by T-5).

(3) Solution viscosity copolymer methyl ethyl ketone-toluene (weight ratio 1/
The viscosity of the 20% by weight resin solution obtained by dissolving in the mixed solvent of 1) was measured at 20° C. using a B-type viscometer.

(4) 17 parts by weight of a pigment dispersible copolymer, 66 parts by weight of a mixed solvent of methyl ethyl ketone toluene (weight ratio 1/1), and titanium oxide as an inorganic pigment (manufactured by Teikoku Kako Co., Ltd., trade name: TR-600A)
) 17 parts by weight were placed in a glass bottle, glass peas in an amount three times the weight of the solid content were added thereto, and the mixture was fed into a paint shaker and dispersed for 60 minutes to prepare an ink vehicle. The obtained ink vehicle was applied onto a hard vinyl chloride resin plate using an applicator and then dried to obtain an ink coating film with a thickness of 15 μm. The obtained ink coating film was supplied to a gloss meter (manufactured by Nippon Denshoku Kogyo Co., Ltd., model: digital variable angle gloss meter VC-ID), and the gloss was measured and used as an index of pigment dispersibility. Note that the higher the gloss value, the better the pigment dispersibility.

(5) Heat-seal resistant neutral high-quality paper (manufactured by KOKUYO Co., Ltd., product name: No 827S-1)
Using an applicator, a resin solution similar to the one used for measuring the solution viscosity was applied four times onto the neutral high-quality paper using an applicator, and then dried to form an ink coating. With the above-mentioned neutral high-quality paper applied to the ink coating surface, it is supplied to a heat seal tester (manufactured by Tester Sangyo Co., Ltd., model 1TP701) and pressed with a heat seal bar under the conditions of a pressure cuff of 0 g/cd and a time of 20 seconds. The highest temperature at which the neutral high-quality paper and the ink coating did not fuse together was measured and used as an index of heat seal resistance.

12 kg of ion-exchanged water, 1 g of hydroxypropylethyl cellulose, and 8.8 g of dilauroyl peroxide were placed in a jacketed, pressure-resistant polymerization vessel equipped with a 25 I2 stirrer.
After charging 45 g of mercaptoethanol and sealing the container to remove residual air, 3.6 kg of vinyl chloride was press-fitted and then heated to 80° C. using a jacket. Immediately after the temperature inside the vessel reached 80°C, a solution of 25 g of N-cyclohexylmaleimide dissolved in 40 g of acetone was added in an amount of 40 times at 5 minute intervals, and polymerization was carried out with stirring. The reactor was cooled for 5 minutes after the final addition, and after cooling, the remaining unreacted vinyl chloride was discharged outside the reactor, and the polymerization slurry was then taken out, washed with ion-exchanged water, and dried to obtain a copolymer. The degree of polymerization and composition of the obtained copolymer were measured and the results are shown in Table 1.

Next, the obtained copolymer was dissolved in a mixed solvent of methyl ethyl ketone and toluene (weight ratio 1/1) to give a concentration of 25% by weight.
A copolymer solution was prepared to obtain a vinyl chloride resin ink vehicle. Using the obtained vinyl chloride resin ink vehicle, various physical properties of the ink vehicle were measured based on the measurement method described above, and the results are shown in Table 1.

As shown in Table 1, a copolymer obtained in the same manner as in Example 1 was used, except that the type and amount of the composition in the copolymer were changed. A vinyl chloride resin ink vehicle was obtained in the same manner.

After measuring the composition and degree of polymerization of the obtained copolymer, using the obtained vinyl chloride resin ink vehicle, the physical properties of the ink vehicle were measured in the same manner as in Example 1, and the results are shown in Table 1. .

A vinyl chloride resin-based ink vehicle was obtained in the same manner as in Example 1, using a vinyl chloride-vinyl acetate copolymer (manufactured by Union Carbide Co., trade name: Vinyl-VYHH) as a copolymer.

Using the obtained vinyl chloride resin ink vehicle, the physical properties of the ink vehicle were measured in the same manner as in Example 1, and the results are shown in Table 1.

A vinyl chloride resin ink vehicle was obtained in the same manner as in Example 1 using a vinyl chloride-vinyl acetate-vinyl alcohol copolymer (manufactured by Union Carbide Co., trade name: VINYLITE VAGH) as the L1-J copolymer.

Using the obtained vinyl chloride resin ink vehicle, the physical properties of the ink vehicle were measured in the same manner as in Example 1, and the results are shown in Table 1.

(The following is a blank space) Copolymer obtained in the same manner as Example 1 except that the type and amount of the composition in the copolymer were changed as shown in Table 2. A vinyl chloride resin ink vehicle was obtained in the same manner as in Example 1.

After measuring the composition and degree of polymerization of the obtained copolymer, using the obtained vinyl chloride resin ink vehicle, the physical properties of the ink vehicle were measured in the same manner as in Example 1, and the results are shown in Table 2. .

(Blank below) (Effect of the invention) The composition of the vinyl chloride resin ink vehicle of the present invention is as described above, and since it is a copolymer of a specific amount of vinyl chloride and an N-substituted maleimide, the above copolymer When the combined product is dissolved in an organic solvent, the viscosity of the solution becomes low, and the dispersibility of the inorganic pigment becomes excellent. Furthermore, it also shows excellent performance in terms of heat seal resistance.

In the second invention of the present invention, the polymerizable polymer further contains at least one selected from the group consisting of a hydroxyl group, a carboxyl group, a sulfonic acid group, a sulfonic acid group, a phosphoric acid group, a quaternary ammonium base, and an amino group. Since the monomers are copolymerized, a vinyl chloride resin ink vehicle with better inorganic pigment dispersibility can be obtained.

Therefore, the vinyl chloride resin-based ink vehicle of the present invention can be used in a wide range of applications such as Clavia printing ink, flexographic printing ink, and screen printing ink.

Claims (1)

[Scope of Claims] 1. A copolymer of (a) vinyl chloride and (b) N-substituted maleimide, comprising 50 to 99% by weight of component (a), (
b) A vinyl chloride resin ink vehicle comprising 1 to 50% by weight of a vinyl chloride resin and an organic solvent. 2, selected from the group consisting of (a) vinyl chloride, (b) N-substituted maleimide and (c) hydroxyl group, sulfonic acid group, sulfonic acid group, carboxyl group, phosphoric acid group, quaternary ammonium base and amino group A copolymer with a polymerizable monomer containing at least one kind, the component (a) being 50 to 98% by weight.
, component (b) is 1 to 50% by weight and component (c) is 0.
A vinyl chloride resin ink vehicle comprising 05 to 10% by weight of a vinyl chloride resin and an organic solvent.