JPS61281119A - Photo-setting oligomer and production thereof - Google Patents

Abstract

PURPOSE:The titled oligomer, containing a reaction product of (meth)acrylic acid with rosin glycidyl ester, diisocyanate and reaction product of (meth)acrylic acid with a diepoxide, having improved curing rate, flexibility, etc., and useful for printing ink, etc. CONSTITUTION:An oligomer obtained by incorporating (A) a reaction product of (meth)acrylic acid with rosin glycidyl ester with (B) a diisocyanate, e.g. isophorone diisocyanate, (C) a reaction product of (meth)acrylic acid with a diepoxide, e.g. 1,6-hexanedol diglycidyl ether and, as necessary, (D) a hydroxyl group-containing acrylic acid ester.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel photocurable oligomer and a method for producing the same. More specifically, the present invention relates to a photocurable oligomer that is a polyfunctional oligomer having ultraviolet curability and is particularly suitable as a binder for printing ink, and a method for producing the same.

The photocurable oligomer of the present invention can be suitably used as a binder for printing ink, and can also be used as a binder for overprint varnish, a binder for paint, a solder resist, etc. In the present layer, the binder for ink 1 is used. Let me represent you and explain.

[Prior Art] Conventionally, ultraviolet curable inks have been produced by adding a reactive diluent such as trimethylolpropane triacrylate to an unsaturated epoxy resin ester, which is obtained by reacting an epoxy resin with acrylic acid, and a photosensitizer. It is known as a composition obtained by appropriately blending pigments and pigments. Among these, unsaturated epoxy resin esters, unsaturated polyester resins, etc. are positioned as polyfunctional oligomers in binders for inks. It is particularly important among the above-mentioned components because it is closely related to the properties of Recently, even UV-curable inks are required to have the same level of printability as conventional solvent-based inks, and conventional polyfunctional oligomers such as unsaturated epoxy resins can fully satisfy this requirement. There is no chinoha.

Therefore, there is a demand in the art for the development of novel multifunctional oligomers that can provide ultraviolet curable inks with excellent printability.

[Problems to be Solved by the Invention] The present invention has been made in order to solve the above-mentioned problems that could not be solved by the prior art.

Therefore, the present inventors took into consideration not only printability but also curing speed, hardness and flexibility of the printed film, and on-machine stability. As a result of extensive research aimed at developing oligomers, it was finally discovered that the above-mentioned problems could be solved by using a specific polyfunctional oligomer having a rosin component in its side chain. The present invention was completed based on this new knowledge.

[Means for Solving the Problems 1] The present invention provides a reaction product of (meth)acrylic acid and rosin glycidyl ester (hereinafter referred to as component (d)), diisocyanates (hereinafter referred to as component (b)), ( meth) a reaction product of acrylic acid and diepoxides (hereinafter referred to as (C1 component)), and optionally cd) a hydroxyl group-containing acrylic ester (hereinafter referred to as component (d))'. The present invention relates to a photocurable oligomer and a method for producing the oligomer.

[Example] In the present invention, a photocurable oligomer can be obtained by adding component (d), component +b>, component (C), and optionally component (d).

The component (d) is a reaction product of (meth)acrylic acid and rosin glycidyl ester, and has the general formula: CO3-CH ■ -C O ++ CH2-0H-OCHN-A -N -C- It is represented by 0ε CH2 0[E]-(-CHats, B represents a rosin residue). The rosins used here are determined by considering the ultraviolet curing speed of the resulting ink and the color tone of the photocurable oligomer, and are usually hydrogenated rosins, disproportionated rosins, etc. that stabilize conjugated double bonds. Treated rosin is suitable.

The component (b) is a diisocyanate, and any conventionally known one can be used as is. Specific examples of these include isophorone diisocyanate, diphenylmethane diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, and phenylene diisocyanate-1. However, in order to obtain a compound having a free isocyanate group at the terminal with high purity by selectively participating in the reaction with one of the isocyanate groups in component (b) in the reaction with component (d), it is necessary to ) It is desirable that the isocyanate groups present in the components are not equivalent. Considering this point, isophorone diisocyanate and tolylene diisocyanate are preferred among the above.

The component (C) is a reaction product of (meth)acrylic acid and diepoxides, and has the general formula [■]: RI
R2CH2-C
C-C)+2゜5sashi.

(In the formula, R1 and R2 are hydrogen atoms or methyl groups, CI (
3 -O-+CH2CH20-+-rff- (m is 1 to 10
is a vine diacrylate represented by (integer), number), Here, the geloxides have the general formula [■]: (wherein, D is -〇-+
CH2CHO+#CH3 (p is an integer from 1 to 15), 10→CI% CH2Otm (II is an integer from 1 to 10), and more specifically, 1.6-hexanethiol Examples include diglycidyl ether, tripropylene diglycidyl ether, polypropylene diglycidyl ether, higher dibasic acid diglycidyl ni-chill, gosofe, l-A type diglycidyl ether, and the like.

The component (d) refers to various acrylic acid ester monomers containing water Fll, and specific examples include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate-1, or General formula [■]
Examples include monomers represented by: (wherein R3 represents a propyl group, butyl group, phenyl group, etc., and R4 represents a hydrogen atom or a methyl group).

Next, a method for producing the photocurable oligomer of the present invention will be explained.

First, to explain the method for producing the constituent components of the oligomer, component (d) is obtained by esterifying (meth)acrylic acid and rosin glycidyl ester. Known compounds such as quaternary ammonium salts and polymerization inhibitors such as phenols, quinones, and phenothiazines can be appropriately selected and used. The molar ratio of (meth)acrylic acid to rosin glycidyl ester is 1:1 chemically, but it may range from 1:0.9 to 1.1 industrially. The amount of the esterification catalyst used is 0.1 to 2 parts (parts by weight, the same applies hereinafter) based on the total amount of (meth)acrylic acid and rosin glycidyl ester, and the amount of the esterification agent used is The amount is preferably 0.001 to 0.5 parts based on the total amount. The reaction temperature is usually 80 to 130°C, and the reaction time is determined by monitoring the acid value of the product, and is usually 3.
~10 hours.

Component (C) consists of (meth)acrylic acid and the general formula [11
It is obtained by an esterification reaction with geloxides represented by (1). In this reaction, the same esterification catalysts and polymerization inhibitors as those used in the production of component ((2)) can be used. (meth)acrylic acid and The charging molar ratio with geloxides is stoichiometrically 2:1, but industrially it may be within the range of 2:0.9 to 1.1.

The oligomer of the present invention can be produced by blending the various components thus obtained according to the following method.

That is, the component (d) and, if necessary, the +cb
A compound having a free isocyanate group at the end is obtained by adding and reacting the C1 component in the presence of the C1 component, and then reacting the compound with the C1 component to obtain an oligomer.

In the case where component (b) is added and reacted in the presence of component (d) and optionally component (d), the molar ratio of the former and (b+acid component) is 1 in chemical diurnal terms; 1, but industrially it may be within the range of 1: 0.9 to 1.1.Since this reaction is essentially a reaction between an isocyanate group and a hydroxyl group, the isocyanate of component (b) If the reactivity of the groups is equivalent, (a
Since the J minor component or component (d) reacts, it is not always easy to selectively leave free isocyanate groups at the end of the molecule, resulting in the production of some by-products.

However, if tolylene diisocyanate, isophorone diisocyanate, or the like is used as the component, the desired intermediate can be easily obtained because of the difference in reactivity of both isocyanate groups. The reaction conditions at this time are appropriately determined by monitoring the NC0 value, and usually the reaction concentration is in the range of 60 to 100°C and the reaction time is in the range of 1 to 5 hours. Next, the intermediate and component (C) are reacted, but in such a case, the same conditions as those for producing the intermediate can be set, and in this case, the molar ratio of the intermediate and component (C1) .2~0.9;1
And it is sufficient. If the charging molar ratio is about 1:1, it will mainly be a trifunctional oligomer, and if the molar ratio is about 2:1.
In this case, the oligomer is mainly a tetrafunctional oligomer.

The present invention will be described in detail below with reference to Synthesis Examples, Examples, and Comparative Examples, but the present invention is not limited to these examples.

Synthesis Example 1 (Rosin Epoxy Acrylate) A sjl volume flask equipped with a stirrer, thermometer, condenser and nitrogen inlet tube was replaced with nitrogen gas, and then 2568 parts (5.81 mol) of disproportionated rosin monoglycidyl ester, HX (wt%, same below) acrylic acid 427 parts (5.81 mol),
As an esterification catalyst, 3.0 parts of benzyltrimethylammonium chloride (hereinafter referred to as BTHAC) (101,000 pp per total feedstock), 3.0 parts of polymerization inhibitor 4-methoxyphenol (hereinafter referred to as HEHQ), and 3.0 parts of phenothiazine were used. Preparation, 105-11 under nitrogen flow
The reaction was completed over 6 hours at 0°C. The acid value of the reaction product was 4.8, and the appearance was brown and transparent balsamic.

Synthesis Examples 2 to 6 (Bifunctional acrylic ester compounds) In Synthesis Example 1, at least one of the type and amount of epoxy compound, acrylic me, BTHACI, amount of phenothiazine, HEHQffi, and reaction time was adjusted as shown in Table 1. Various bifunctional acrylic ester compounds were obtained in the same manner as in Synthesis Example 1 except for the following changes.

Example 1 11 equipped with a stirrer, thermometer, cooler and nitrogen inlet tube
After replacing the air with nitrogen gas, a volumetric flask was charged with 228.6 parts of rosin epoxy acrylate obtained in Synthesis Example 1 and 98 parts of isophorone diisocyanate (hereinafter referred to as IPDI).
．． Prepare 9 parts, HEHQ 0.525 parts, 15-80
After reacting at °C for 1 hour, 197.5 parts of the bifunctional acrylic ester compound obtained in Synthesis Example 2 was charged, and the reaction was continued for an additional 1 hour. Next, two drops of octyl stannous as a urethanization catalyst were added, and the mixture was stirred and reacted at the same temperature for 3 hours to obtain an oligomer.

The performance of the clear cured film of the obtained oligomer and its performance as an ultraviolet curable printing ink were evaluated by the following evaluation method, and the results are shown in Tables 3 and 4.

Examples 2 to 8 In Example 1, the user of rosin epoxy acrylate, the type and amount of diisocyanate, the type of bifunctional acrylic ester compound (bifunctional acrylic ester compound shown in Synthesis Examples 2 to 6) and its Example 1 except that at least one of the amounts was changed as shown in Table 2.
Various oligomers were obtained in the same manner as above.

We evaluated the performance of these oligomers and reported the results in the third section.
Shown in Table and Table 4.

Example 9 Using the same reaction apparatus as in Example 1, 136.4 parts of the oligomer obtained in Example 1, 3088 parts of 2-human 0-oxyethyl acrylate, 118.0 parts of IPDI, HEH
After charging 0.4 parts of Q and reacting at 75 to 80°C for 1 hour, 197.5 parts of the bifunctional acrylic ester compound obtained in Synthesis Example 3 was charged, and the reaction was continued for an additional 1 hour. Then, two drops of octyl stannous were added, and the mixture was stirred at the same temperature for 3 hours to react and obtain an oligomer.

Performance evaluation was performed on the oligomer and the results were reported in the third
Shown in Table and Table 4.

(Performance evaluation of clear cured film) 1. Preparation examples of cured film, 80 parts of various oligomers obtained in Synthesis Example 5 (Comparative Example 1) and Synthesis Example 6 (Comparative Example 2), 20 parts of trimethylolpropane triacrylate , Darocure-117
3 (manufactured by Merck & Co., Ltd., 2-hydroxy-2-methyl-1-phenylpropan-1-one) and coated on a tin plate with a bar coater to a film thickness of 20 mm under the following curing conditions. It is cured by irradiating it with ultraviolet light.

80111/cmx I lamp, distance 10cm between UV lamp
, irradiation time 0025 seconds 2 Performance evaluation method Curing speed: Time required for curing (seconds) Film hardness: Pencil hardness based on JIS-5400 Flexibility: Flexibility bending test based on JIS-5400 Film strength : Impact test based on JIS-5400 (
Performance evaluation as ultraviolet curable printing ink) 1. Various polyfunctional oligomers obtained in ink processing Examples 1 to 9 and Comparative Examples 1 to 2, Carmine 6B, trimethylolpropane triacrylate, Darocure-1173, 14EHQ
were mixed in the proportions shown in Table 3, kneaded with three rolls, and the tack value measured with an incometer was 11 to 1.
3. Get various inks.

2 Ink performance evaluation method Curing property (curing time): Ink 0.69 was tested using R1 tester (
■Mei Seisakusho) was used to spread the color onto carton paper, and immediately irradiated with ultraviolet light from a distance of 10cm using an 801/cm high-pressure mercury lamp.
The curing time is determined as the irradiation time (seconds) required until the ink stops adhering to the paper.

Gloss of Raw Ink and Emulsified Ink 2 The gloss of the cured printed matter obtained above (original ink gloss) was evaluated by visual observation. In addition, after emulsifying 0.6 g of ink and dampening water using an R1 tester and draining the water, the color was spread on carton paper and cured under the same conditions as when measuring the gloss of the original ink. The gloss is similarly observed with the naked eye and evaluated according to the following criteria.

◎: Very good O: Good Δ: Intermediate between O and Check with the naked eye the condition of the ink scattered on the
! and evaluate them using the following criteria.

O: Little... Suitable for use. ×: Too much... Not suitable for use. Cleanability: Evaluate the cleanability with kerosene of the ink meter roll to which various inks have adhered.

Storage stability: Put the ink in a glass container, seal it tightly, leave it in an incubator (40°C), and measure the number of days until it polymerizes and solidifies.

[Margins below] [Effects] The polyfunctional oligomer of the present invention obtained as described above has the following properties:
By utilizing its photocurability, it can be applied to a wide range of applications.For example, when used as a binder for printing ink, the curing speed of the resulting printing ink is fast, and it also has excellent gloss, pigment dispersibility, and printability. It has excellent advantages in that it is comparable to conventional solvent-based printing inks in these respects. In addition, it can be suitably used as a binder for overprint varnishes, a binder for paints, a binder resist, etc., and has the effect of maintaining its strength.

(Issuance of procedural amendment) July 3, 1986

Claims (1)

[Claims] 1 (a) a reaction product of (meth)acrylic acid and rosin glycidyl ester, (b) diisocyanates, (c) (
A photocurable oligomer comprising a reaction product of meth)acrylic acid and diepoxides and optionally (d) a hydroxyl group-containing acrylic ester as constituent components. 2. After reacting (a) a reaction product of (meth)acrylic acid and rosin glycidyl ester and optionally (d) a hydroxyl group-containing acrylic ester and (b) diisocyanates to obtain a compound having an isocyanate group at the terminal, A method for producing a photocurable oligomer, which comprises reacting the compound with (c) a reaction product of (meth)acrylic acid and diepoxides.