JP2510012B2 - Chromogenic composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Field of Industrial Application) The present invention is directed to a color-forming composition capable of developing a beautiful color tone without causing addition of components for coloring the polymer itself. Regarding

(Prior Art) In recent years, synthetic polymers have made rapid progress and have come to be used in various forms over an extremely wide range. However, most synthetic polymers have no color by themselves, and it is necessary to add pigments, dyes, etc., or paint the surface for coloring. These coloring means can only express colors within the color tone range of the colorant, and there is little room for providing completely new colors at present with diversifying tastes.

(Problems to be solved by the invention) When the conventional coloring means is viewed from the viewpoint of the characteristics of the polymer material, the pigments used for coloring are a factor that deteriorates the physical and chemical properties, and is a negative factor in terms of quality. Often regarded as

In addition, when a color is given to the polymer itself, the method of adding a side chain having the same chemical structure to the dye in the polymer is expected to impair the properties of the polymer more than blending the dye. Obviously, this will also be extremely unrealistic.

The present invention solves the above-mentioned problems in the conventional coloring with a dye, that is, the disadvantage that the excellent properties of the polymer material are more or less impaired, by forming a color by the polymer itself and eliminating the coloring agent, and , To open up a new color world.

As a result of investigations by the present inventors, a microphase-separated structure having the same size as the wavelength region of visible light is generated in a polymer, and the color is developed by interference of light, whereby a color is obtained without using dyes. Find that it is possible to give
The present invention has been achieved.

It is well known that the color of monodisperse latex develops on the same principle, and there are some examples of immobilization such as artificial opal, but a complicated procedure is required, and in this case, it can be called a polymer pigment. However, there is no requirement for any function other than color, and it is distinct from the present invention in which it can be fixed in the form of a film, a molded product, a fiber, a coating film, etc., if necessary. As described above, the present invention solves the above-mentioned various drawbacks and provides a new color world for synthetic resin products.

[Structure of Invention]

The present invention relates to DL-2-hydroxy-n-butyric acid, DL-3-
Hydroxy-n-butyric acid, hydroxypivalic acid, 12-
Compound (A) containing a hydroxyl group and a carboxyl group selected from hydroxystearic acid, salicylic acid and p-hydroxybenzoic acid, a cyclic acid anhydride (B), and epichlorohydrin, phenylglycidyl ether, glycidyl (meth) acrylate, glycidylcinnamate, When an epoxide (C) selected from allyl glycidyl ether, vinylcyclohexene monoepoxide and 1,3-butadiene monoepoxide is present in the presence of a tertiary amine catalyst and the cyclic acid anhydride (B) is a dicarboxylic acid anhydride, , 1 to 10 mol of the cyclic acid anhydride (B) and 1 to 10 mol of the epoxide (C) with respect to 1 mol of the compound (A), and the epoxide (C) to the cyclic acid anhydride (B). When the cyclic acid anhydride (B) is a tricarboxylic acid anhydride in approximately equimolar ratio, the compound is (A) 1 mole of cyclic acid anhydride (B) and 1 to 20 moles of epoxide (C), and 1 mole of cyclic acid anhydride (B) to epoxide (C). Polyester (E) obtained by reacting at a ratio of about 1 to 2 moles, and dimethylaminoethyl methacrylate, acrylic acid, methacrylic acid, alkyl acrylate, alkyl methacrylate, styrene, vinyl acetate, vinyl propionate, vinyl ether, 3 to 20 in monomers selected from acrylonitrile
It is a color-forming composition obtained by reacting an acrylic polymer (F) having a tertiary amino group, which is contained and copolymerized in an amount of mol%.

Although the coloring principle of the coloring composition of the present invention is not always clear, it may be due to the formation of a microphase-separated structure due to the compatibility problem between the acrylic polymer as the main chain and the polyester as the graft chain. Conceivable. In other words, it seems to have a structure similar to that of a stabilizer-stabilized latex in which several polyester chains are associated to form a spherical core, and an acrylic polymer chain, which is the main chain, is arranged around it. Be done.

In this case, it is considered that the color development requires that the cores have a uniform particle size and have a regular arrangement at appropriate intervals, and it is expected that the present composition is suitable for satisfying the requirement. In the present invention, the compound (A) containing at least one hydroxyl group and at least one carboxyl group includes DL-2-hydroxy-n-butyric acid, DL-3-hydroxy-n-butyric acid, hydroxypivalic acid and 12-hydroxystearin. Acid, salicylic acid, p-hydroxybenzoic acid, etc.

In the present invention, the cyclic acid anhydride (B) is an intramolecular anhydride of polyvalent carboxylic acid, and is a saturated or unsaturated aliphatic polyvalent carboxylic acid anhydride, alicyclic polyvalent carboxylic acid anhydride, aromatic There are polyvalent carboxylic acid anhydrides, etc., or some of these substituted with saturated or unsaturated hydrocarbon groups, aromatic ring groups, halogen atoms, heterocyclic groups, etc. Succinic acid, phthalic anhydride,
Maleic anhydride, itaconic anhydride, glutaric anhydride, dodecenyl succinic anhydride, chlorendecic anhydride, pyromellitic anhydride, trimellitic anhydride, cyclopentanetetracarboxylic dianhydride, hexahydrophthalic anhydride,
Methylhexahydrophthalic anhydride, tetramethylene maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, 5- (2,5-dioxotetrahydroxy Frill)-
3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, methyl nadic acid anhydride, benzophenone tetracarboxylic acid anhydride, ethylene glycol bis (anhydrotrimellitate), glycerol tris (anhydrotrimellitate), etc. is there. Among these, it is preferable to use a dicarboxylic acid anhydride that does not form a crosslinked structure.

In the present invention, examples of the epoxide (C) include epichlorohydrin, phenylglycidyl ether, glycidyl (meth) acrylate, glycidyl cinnamate, allyl glycidyl ether, vinylcyclohexene monoepoxide, and 1,3-butadiene monoepoxide, which are saturated. Alternatively, it may be substituted with an unsaturated hydrocarbon group, aromatic ring group, halogen atom, heterocyclic group or the like.

In the present invention, as the tertiary amine (D) which is a catalyst for reacting the compound (A) containing one or more hydroxyl groups and one or more carboxyl groups, the cyclic acid anhydride (B) and the epoxide (C), triethylamine, Tertiary amines such as tributylamine, N, N-diethylaniline, N, N-dimethylbenzylamine and N, N-dimethylaniline can be used. Furthermore, when an epoxide (C) having an ethylenically unsaturated group is used, radical polymerization of hydroquinone, hydroquinone monomethyl ether, tert-butylcatechol, p-benzoquinone or the like is performed in order to keep the unsaturated group stable during the reaction. It can be performed with an inhibitor added.

The reaction starts with 1 hydroxyl group and 1 carboxyl group, respectively.
First, the hydroxyl group of the compound (A) containing at least one and the acid anhydride group of the cyclic acid anhydride (B) react preferentially, and then,
The carboxyl group generated by this reaction and the epoxy group of the epoxide (C) react to generate a secondary hydroxyl group. Furthermore, the reaction similar to the above can be successively performed such that the generated hydroxyl group reacts with the acid anhydride group of the cyclic acid anhydride (B), and it contains at least one hydroxyl group and at least one carboxyl group. By adjusting the amounts of the cyclic acid anhydride (B) and the epoxide (C) reacted with the amount of the compound (A), the amount of the compound (A) containing at least one hydroxyl group and at least one carboxyl group is reduced to less. It is possible to form a polyester chain having a desired length.

When the cyclic acid anhydride (B) is a dicarboxylic acid anhydride, 1 to 10 mol of the cyclic acid anhydride (B) is contained per 1 mol of the hydroxyl group of the compound (A) containing at least one hydroxyl group and at least one carboxyl group. , And epoxide (C) in an amount of 1 to 10 mol, and the epoxide (C) is reacted with the cyclic acid anhydride (B) in an approximately equimolar ratio. When the cyclic acid anhydride (B) is a tricarboxylic acid anhydride, 1 to 10 mol of the cyclic acid anhydride (B) is contained per 1 mol of the hydroxyl group of the compound (A) containing at least one hydroxyl group and at least one carboxyl group. It is preferable that the epoxide (C) is reacted at a ratio of 1 to 20 mol, and the epoxide (C) is reacted at a ratio of about 1 to 2 mol with respect to 1 mol of the cyclic acid anhydride (B).

When the amount of the cyclic acid anhydride (B) reacted with 1 mol of the hydroxyl group of the compound (A) containing one or more hydroxyl groups and one or more carboxyl groups is less than 1 mol, the microgel formation of the obtained resin is unsuccessful. If the amount of the cyclic acid anhydride (B) exceeds 10 mol, the unreacted cyclic acid anhydride (B) and the epoxide (C) may remain and the color may not be sufficiently developed. The resin tends to be turbid due to, for example, poor compatibility with the acrylic polymer having a primary amino group.

In the present invention, as the acrylic polymer (F) having a tertiary amino group, 2-dimethylaminoethyl methacrylate, acrylic acid, methacrylic acid, alkyl acrylate, alkyl methacrylate, styrene, vinyl acetate, vinyl propionate, vinyl ether, acrylonitrile , And the like.

2-Dimethylaminoethyl methacrylate is preferably used in an amount of 3 to 20 mol% in the acrylic polymer (F).

Examples of alkyl (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and octyl (meth) acrylate.

The reaction is a normal radical polymerization and does not impose any limitation on the reaction method, but a solution reaction is preferable from the viewpoint of directly moving to the next reaction and the ease of control of the reaction.

As a solvent used for forming a solution, any solvent having solubility such as methyl ethyl ketone, toluene, cellosolve, ethyl acetate, etc. may be used, and a single solvent or a mixture of a plurality of solvents may be used.

Mixing the obtained polyester resin composed of a cyclic acid anhydride (B) having a compound (A) containing at least one hydroxyl group and at least one carboxyl group and an epoxide (C) with an acrylic polymer having a tertiary amine group. Then, the desired color forming composition is obtained by heating and stirring.

Furthermore, in the present invention, when the epoxide (C) having an ethylenically unsaturated group is used, the polyester part has an unsaturated group, and the electron beam curing or the ultraviolet curing / thermosetting by combination with an appropriate radical generator is carried out. By the curing method of
Can be easily solidified.

Radical generators for UV curing include benzoin, benzoin methyl ether, benzoin ethyl ether, o-benzoyl benzoic acid methyl-p-benzoin ethyl ether, benzoin isopropyl ether, α
-Benzoins such as methylbenzoin, dimethylbenzyl ketal, trichloroacetophenone, acetophenones such as 2,2-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-
Propiophenones such as 4'-isopropyl-2-methylpropiophenone, α-acyloxime ester, benzophenone, methylbenzophenone, p-chlorobenzophenone, benzophenones such as p-dimethylaminobenzophenone, 2-chlorothioxanthone, 2 -Ethylthioxanthone, 2-isopropylthioxanthone and other thioxanthones, benzyl, dibenzosuberone, etc.,
Kiyomi Kato: "UV / EB Curing Handbook-Raw Materials-"
(December 1985, published by Kobunshi Publishing Co., Ltd.), pp. 67-73 or Fuzo Yamashita, Tosuke Kaneko, "Handbook of Crosslinking Agents" (1981)
October, published by Taiseisha) pp. 582-593. Similar to other UV curable resins, it is also effective to use a radical generation accelerator together. Examples of such accelerators include 4,4′-bis (diethylamino) benzophenone, N-dimethylaminoethyl benzoate, In addition to dimethylethanolamine, glycine, etc., Kiyomi Kato edition: Ibid.
Those described on pages 67 to 73 can be used.

Further, as a radical generator in the case of heat curing, benzoyl peroxide, acetyl peroxide, methyl ethyl ketone peroxide, lauroyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, tert-butyl hydroperoxide, cumene Organic peroxides such as hydroperoxide and azo radical generators such as azobisisobutyronitrile and azobisvaleronitrile are used. Here, when an organic peroxide having a low radical generation rate is used, tributylamine, triethylamine, dimethyl-p-toluidine, dimethylaniline, triethanolamine,
Tertiary amines such as diethanolaniline or metallic soaps such as cobalt naphthenate, cobalt octoate and manganese naphthenate can be used as accelerators.

The radical generator described above is usually used in an amount of 0.05 to 20 parts, preferably 0.5 to 10 parts, per 100 parts by weight of the total amount of the compound having an unsaturated double bond in the color forming composition of the present invention. Used in proportion.

In order to further strengthen the structure after curing, in the color forming composition of the present invention, in addition to the radical generator and the accelerator, a monomer having an ethylenically unsaturated group such as a (meth) acryloyl group. Or an oligomer can be added. Examples of such monomers or oligomers include styrene, alkyl (meth) acrylate, (meth) acrylic acid, polyhydric alcohol poly (meth) acrylate, epoxy poly (meth) acrylate, oligoester poly (meth) acrylate, polyurethane poly ( (Meth) acrylate, diallyl phthalate, diallyl isophthalate and the like.

The color-forming composition of the present invention contains pigments, dyes, inorganic fillers such as mica, metal powders such as silver powder, copper powder, nickel powder, carbon black, graphite, etc. A silane coupling agent or an isocyanate compound such as tolylene diisocyanate or isophorone diisocyanate can be added.

Of course, it is not preferable to use the second component from the viewpoint of the purpose of the present invention that a color is formed without adding a dye or the like, but if it is used in an effective amount, the range of color tone can be increased or the function can be improved. It is possible to do.

The color-forming composition of the present invention may be used as a paint or an adhesive in a solution state and then cured by ultraviolet rays, electron beams, heat, etc., and the solvent is removed to give a film, a fiber, a molded article or the like. It may be cured after curing, or may be processed after curing.

(Examples) Hereinafter, the present invention will be described with reference to Examples. In the examples, “part” means “part by weight” and “%” means “% by weight”.

Example 1 Synthesis of acrylic polymer having tertiary amino group Butyl acrylate 94.0 parts Dimethylaminoethyl methacrylate 6.0 parts Azobisisobutyronitrile 0.3 parts Ethyl acetate 230.0 parts Mixture 165 parts of the above composition heated to 80 ° C. 165 parts of the mixture was added dropwise, and after completion of the addition, the mixture was heated under reflux for 12 hours and cooled to obtain a solution of an acrylic polymer containing a tertiary amino group (solid content: 30%).

Synthesis of polyester p-Hydroxybenzoic acid 41.1 parts Hexahydrophthalic anhydride 138.6 parts Phenylglycidyl ether 127.9 parts N, N-Dimethylbenzylamine 2.7 parts The above compositions are mixed and reacted at 80 ° C. for 6 hours, and then ethyl acetate 718. Parts were added to obtain a polyester resin solution (solid content: 30%).

Obtained solution of acrylic polymer containing tertiary amino group
Mix 100 parts and 21.3 parts of polyester resin solution, and mix at 20
The mixture was heated and stirred for a time to obtain a color forming resin solution.

This resin solution was translucent and had a yellowish green pearl luster, and the transmitted light was wine red.

Example 2 Synthesis of Acrylic Polymer Having Tertiary Amino Group Butyl acrylate 94.0 parts Dimethylaminoethyl methacrylate 6.0 parts Azobisisobutyronitrile 0.3 parts Ethyl acetate 230.0 parts Mixture 165 parts of the above composition heated to 80 ° C. 165 parts of the mixture was added dropwise, and after completion of the addition, the mixture was heated under reflux for 12 hours and cooled to obtain a solution of an acrylic polymer containing a tertiary amino group (solid content: 30%).

Polyester synthesis p-Hydroxybenzoic acid 41.1 parts Hexahydrophthalic anhydride 138.6 parts Glycidyl methacrylate 127.9 parts N, N-Dimethylbenzylamine 2.7 parts Hydroquinone 5.5 parts The above composition is mixed and reacted at 80 ° C. for 6 hours, followed by acetic acid. 718 parts of ethyl was added to obtain a solution (solid content: 30%) of a polyester resin having an ethylenically unsaturated group in its side chain.

Obtained solution of acrylic polymer containing tertiary amino group
Mix 100 parts and 21.3 parts of polyester resin solution, and mix at 20
The mixture was heated and stirred for a time to obtain a color forming resin solution.

When the obtained solution of the resin having an ethylenically unsaturated group in the side chain was spread on a glass plate and the solvent was volatilized to form a dry film, the same color tone as in Example 1 was exhibited. Furthermore, when this dried film was irradiated with an electron beam of 10 megarads using an electron curtain type electron beam irradiator (B-150-15-10L type manufactured by Energy Science Co., Ltd.), a hard film was formed.
No change in hue was observed.

[Effects of the Invention] The color-forming composition of the present invention, as shown in the above Examples,
Only the usual radical polymerization and graft reaction are combined, and no other complicated operations are required.

Accordingly, a color-forming polymer can be obtained very easily, and new color possibilities are offered in the field of synthetic polymer products.

Claims (2)

(57) [Claims] 1. DL-2-hydroxy-n-butyric acid, DL-3-
Hydroxy-n-butyric acid, hydroxypivalic acid, 12-
Compound (A) containing a hydroxyl group and a carboxyl group selected from hydroxystearic acid, salicylic acid and p-hydroxybenzoic acid, a cyclic acid anhydride (B), and epichlorohydrin, phenylglycidyl ether, glycidyl (meth) acrylate, glycidylcinnamate, When an epoxide (C) selected from allyl glycidyl ether, vinylcyclohexene monoepoxide and 1,3-butadiene monoepoxide is present in the presence of a tertiary amine catalyst and the cyclic acid anhydride (B) is a dicarboxylic acid anhydride, , 1 to 10 mol of the cyclic acid anhydride (B) and 1 to 10 mol of the epoxide (C) with respect to 1 mol of the compound (A), and the epoxide (C) to the cyclic acid anhydride (B). When the cyclic acid anhydride (B) is a tricarboxylic acid anhydride in approximately equimolar ratio, the compound is (A) 1 mole of cyclic acid anhydride (B) and 1 to 20 moles of epoxide (C), and 1 mole of cyclic acid anhydride (B) to epoxide (C). Polyester (E) obtained by reacting at a ratio of about 1 to 2 moles, and dimethylaminoethyl methacrylate, acrylic acid, methacrylic acid, alkyl acrylate, alkyl methacrylate, styrene, vinyl acetate, vinyl propionate, vinyl ether, 3 to 20 in monomers selected from acrylonitrile
A color forming composition obtained by reacting an acrylic polymer (F) having a tertiary amino group, which is contained by mole% and copolymerized. 2. The color-forming composition according to claim 1, wherein the epoxide (C) is an epoxide having an ethylenically unsaturated group.