JPS62185050A - Hydroxyl group-containing (meth)acrylate - Google Patents

Abstract

NEW MATERIAL:A (meth)acrylate shown by formula I [R is H or CH3; Z is 2-8C bifunctional organic group; (A) is ring opening group of compound shown by formula II; (B) is ring opening group of cyclic compound except compound shown by formula II; l is 1-20 integer; m is 0-20 integer; (A) and (B) are arbitrarily arranged]containing a hydroxyl group and at least one alkenyl group in the molecule. EXAMPLE:A hydroxyl group-containing acrylate shown by formula III. USE:Having a wide use for coating compounds, adhesives, fiber modifying materials, radiation curing type resins, etc. PREPARATION:Hydroxyl group of a compound shown by formula III and a compound shown by formula II and, if necessary, a cyclic compound except the compound shown by formula II are subjected to addition reaction in the presence of preferably a catalyst, especially heteropoly-acid to give a compound shown by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to hydroxyl group-containing acrylate or methacrylate (hereinafter abbreviated as hydroxyl group-containing (meth)acrylate) K. More specifically, it relates to novel (meth)acrylates containing a hydroxyl group and at least one alkenyl group in the molecule.

[Conventional technology]

Hydroxyacrylate or hydroxymethacrylate (hereinafter hydroxy(meth)) such as hydroxyethyl acrylate or hydroxyethyl methacrylate
Abbreviated as acrylate. ) to which ethylene oxide or propylene oxide is added are known polyalkylene glycol mono(meth)acrylates. i9, C-caprolactone modified hydroxy(meth)acrylate with ε-caprolactone added
Acrylates are also known. Furthermore, we have added hydroxyl group-containing (meth)acrylates with butylglycidyl ether and phenylglycidyl ether (
Meta)acrylates are also known. These known hydroxyl group-containing (meth)acrylates are used in paints, fiber modifiers, etc. by homopolymerization or copolymerization with other vinyl monomers, as well as incyanates, epoxy compounds, acid anhydrides, etc. It is used for various purposes by reacting with.

[Problem that the invention seeks to solve]

However, from the table, all of these utilize the reactivity of hydroxyl groups and (meth)acryloyl groups.

Therefore, the uses of these known hydroxyl group-containing (meth)acrylates appear to be limited, and there is currently a desire to develop vinyl monomers with novel structures.

[Means and effects for solving the problems] As a result of intensive studies on the current state of the art, the present inventors have arrived at a hydroxyl group-containing (meth)acrylate having a novel structure. These hydroxyl group-containing (meth)
Acrylates have three types of reactive groups in their molecules: hydroxyl groups, (meth)acryloyl groups, and alkenyl groups, so they can be homopolymerized or copolymerized with other vinyl monomers to form (co)polymers with terminal hydroxyl groups. After reacting the nine-terminal hydroxyl group with an isocyanate group, epoxy group, or carboxyl group, etc., and then copolymerizing it with other vinyl monomers, or reacting the alkenyl group with thiols, paints,
It has a wide range of applications such as adhesives, fiber modifying materials, and radiation-curable resins. Therefore, an object of the present invention is to provide a novel hydroxyl group-containing (meth)acrylate having a specific structure that can be effectively applied to various uses.

The present invention is based on the general formula [wherein R is a hydrogen atom or a methyl group, Z
represents a divalent organic group having 2 to 8 carbon atoms, 2 represents a ring-opening group of alkenyl glycidyl ethers represented by the following general formula (II), and ■ represents an alkenyl glycidyl group represented by the following general formula (II). Represents a ring-opening group of a cyclic compound excluding ethers, ``o'' is an integer of 1 to 20, and m is 0 or 1 to 20.
is an integer, and the arrangement of the ring-opening group of the alkenyl glycidyl ethers or cyclic compounds represented by . ] This relates to a hydroxyl group-containing (meth)acrylate represented by the following.

In the formula, R1 is a hydrogen atom or a (halo-substituted) hydrocarbon group having 20 or less carbon atoms, and Hz is an alkenyl group having 20 or less carbon atoms. ] As a method for producing a hydroxyl group-containing (meth)acrylate represented by the general formula <1) of the present invention, for example, the general formula % formula % () (wherein R is a hydrogen atom or a methyl group, and 2
represents a divalent organic group having 2 to 8 carbon atoms. ) to the hydroxyl group of the hydroxy(meth)acrylate represented by the above general formula (n) and optionally a cyclic compound other than the alkenyl glycidyl ethers represented by the above general formula (It). One example is how to do it. When employing such a production method, it is desirable to carry out the reaction in the presence of a catalyst. Examples of catalysts include basic catalysts such as organic amines; protonic acids such as sulfuric acid and hydrochloric acid; Lewis acid catalysts such as boron trifluoride, boron trisulfide etherate, tin tetrachloride, and antimony pentoxide; tungstrine. Examples include catalysts made of acids, heteropolyacids such as tungstosilicic acid, tungstoboric acid, molybdophosphoric acid, molybdosilicic acid, or salts thereof. Among these, heteropolyacids exhibit high catalytic activity even at low reaction temperatures, allowing reactions to be carried out at relatively low temperatures, thereby avoiding the risk of thermal polymerization due to vinyl groups in raw materials and reaction products. Furthermore, it is preferable because it produces a highly purified hydroxyl group-containing (meth)acrylate with less by-products such as homopolymers of cyclic compounds and diesters, and does not cause coloring of the product.

General formula % formula % () (wherein, R is a hydrogen atom or a methyl group, Z
represents a divalent organic group having 2 to 8 carbon atoms. ) As a specific example of hydroxy (meth)acrylate,
Examples include hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, hydroxycyclohexyl acrylate, hydroxycyclohexyl methacrylate, and the like. These may be used alone or as a mixture. The compound to be subjected to the addition reaction with the hydroxy(meth)acrylate is a cyclic compound (excluding the alkenyl glycidyl ethers (a) represented by the general formula (n) and, if necessary, the alkenyl glycidyl ethers represented by the general formula (II)). selected from b).

Examples of the (halo-substituted) hydrocarbon group in the alkenyl glycidyl ether (a) represented by the above general formula include hydrocarbons such as alkyl groups, alkenyl groups, aryl groups, hydrogenated aryl groups, and aralkyl groups having 20 or less carbon atoms. at least one hydrogen atom of the group or their hydrocarbon group
Examples include halo-substituted hydrocarbon groups in which each hydrogen atom is substituted with a halogen atom, and of course a group in which all hydrogen atoms are substituted with halogen atoms may be used.

Examples of alkenyl glycidyl ethers (a) are:
Examples include vinyl glycidyl ether, allyl glycidyl ether, butenyl glycidyl ether, and the like.

Cyclic compounds excluding alkenyl glycidyl ethers (b
) (hereinafter abbreviated as cyclic compound (b)). Examples of ethylene oxide, propylene oxide, 1
, 2-butylene oxide, 1,2-epoxydecane, 1
, 2-epoxyhexadecane, etc.; butadiene monoxide, 1,2-epoxy-5
-Alkenyl oxides such as hexene; phenylalkylene oxides such as styrene oxide: 1
, 5-cyclododecadiene-9-10-epoxide, 1
Hydrogenated aryl alkylene oxides such as , 2-epho dicyclododecane, etc.; ε-caprolactone, methyl-
ε-caprolactones such as C-caprolactone;
Tetrahydrofuran; Alkyl glycidyl ethers such as methyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, etc.; Aryl glycidyl ethers such as phenyl glycidyl ether, cresyl glycidyl ether, etc.; Epihalohydrin such as epichlorohydrin, shrimp bromohydrin/etc. Examples include:

alkenyl glycidyl ethers (a) and optionally a cyclic compound (b) to the hydroxy(meth)acrylate;
), the raw material hydroxy (meth)
Addition reaction rate of alkenyl glycidyl ethers (a) and cyclic compound (b) to the hydroxyl group of acrylate and addition reaction rate of alkenyl glycidyl ethers (a) and cyclic compound (b) to the hydroxyl group of hydroxy(meth)acrylate.
When the addition reaction rates of al and cyclic compounds (bl) are almost equal, the addition number distribution of the resulting reaction product shows a statistical distribution, and the raw material hydroxy (meth)acrylate is monotonically distributed in the reaction product. In addition, the upper limit of the number of additions of alkenyl glycidyl ethers (a) and cyclic compounds (b) is determined by the difficulty of obtaining them due to the statistical distribution of the number of additions and the decrease in the proportion of hydroxyl groups in one molecule. Considering the decrease in usefulness, it is 40 moles per mole of hydroxy(meth)acrylate.

Unreacted raw material hydroxy (meth)acrylate can be removed from the product by distillation or extraction if it remains undesirable, but unreacted hydroxy (meth)acrylate is not separated and removed from the product. It can also be used for various purposes in the form of a mixture with hydroxyl group-containing (meth)acrylates.

The hydroxyl group-containing (meth)acrylate in the present invention also includes coaddition modified products. Examples of these include hydroxyl group-containing (metallic) products in which the terminal hydroxyl group of the reaction product is partially modified from a secondary alcohol form to an alcohol form in order to increase the reactivity of the terminal hydroxyl group with isocyanates, epoxy compounds, etc. ) There is acrylate. Specifically, for example, the reaction product obtained by adding alkenyl glycidyl ethers to hydroxy(meth)acrylate is further added with an unsubstituted cyclic compound such as ethylene oxide, tetrahydrofuran, or 6-caprolactone. The terminal hydroxyl group can be modified to improve its reactivity.

As described above, in the hydroxyl group-containing (meth)acrylate of the present invention, it is possible to increase the reactivity of the K-terminated hydroxyl group by forming it into a co-addition modified product.

The bitroxy(meth)acrylate and alkenyl glycidyl ether (a) and if necessary a cyclic compound (b)
The reaction with is preferably carried out at a temperature of -10 to 120°C, particularly 10 to 100°C. When the reaction temperature is high, the polymerization reaction of the vinyl groups of the hydroxy (meth)acrylate as a raw material and the hydroxyl group-containing (meth)acrylate as a reaction product tends to occur. If the reaction temperature is too low, the reaction rate will be low. The reaction does not necessarily need to be carried out at a constant temperature, and the reaction temperature in the first and second half of the reaction can be changed.

Further, in order to avoid polymerization of vinyl groups in the raw materials and reaction products, it is preferable to carry out the reaction in the presence of a polymerization inhibitor. When commercially available hydroxyethyl acrylate or methacrylate is used as a hydroxy(meth)acrylate, a polymerization inhibitor is already added to these esters, but the polymerization inhibitor may be added again during the reaction. Examples of polymerization inhibitors include hydrotetraquinone, hydroquinone monomethyl ether, p-benzoquinone, methylhydroquinone, t-butylhydroquinone, di-t-
Butylhydroquinone, t-butylcatechol, phenothiazine, N,N'-di-2-naphthyl-p-phenylenediamine, 4,6-sinitro-oruzole, N-
Examples include nitrosodiphenylamine, α-naphthol, copper salts, and the like. The amount used is usually o, based on the reaction raw materials.
oos to 1% by weight.

There is no particular restriction on the reaction pressure, and it is preferable to carry out the reaction under normal pressure or slightly increased pressure. The reaction time depends on the type of catalyst used,
Although it depends on the amount added and the reaction temperature, it is generally 1 to 24 hours.

There is no particular restriction on the method of adding the reaction raw materials, and it depends on the type of raw materials, reaction temperature, molar ratio of hydroxy (meth)acrylate to alkenyl glycidyl ether (a) or cyclic compound (b), heating or cooling capacity of the reaction equipment, etc. You can choose as you like. That is, at the start of the reaction, raw materials, catalyst,
A method may be used in which a solvent and a polymerization inhibitor are mixed in advance, or a method in which lfi or two or more of the raw materials are reacted while being added.

For example, when using a substance that generates a large amount of heat during reaction, such as alkylene oxide, it is preferable to carry out the reaction while gradually adding the raw materials. On the other hand, when using a substance such as ε-caprolactone which has a small calorific value during reaction, it is preferable to start the reaction by mixing all the raw materials from the beginning. The reaction method can be carried out either batchwise or continuously. Generally, the reaction can be carried out while blowing an atmospheric gas, and these gases include nitrogen, air, or air diluted with nitrogen gas.

Although the reaction can be carried out without a solvent, it can also be carried out in a solvent. Specific examples of such solvents include ketones such as methyl ethyl ketone, ethers such as dipropyl ether, and hydrocarbons such as benzene, toluene, cyclohexane, hexane, and heftane.

Various methods can be used to purify the reaction product. For example, the reaction product is brought into contact with an adsorbent such as magnesium oxide, aluminum oxide, silicon oxide, magnesilla hydroxide, magnesium silicate, or magnesium alumina hydroxide, or the reaction product is washed with an aqueous alkali solution and dehydrated. In particular, it can also be purified. In the case of alkaline cleaning, in order to reduce the loss of water-soluble products, it is desirable to convert the reaction product into a hydrocarbon solution such as hexane or benzene, and then perform alkali cleaning. After washing with water, the solvent can be removed by distillation or the like to obtain a highly pure product.

Specific examples of the hydroxyl group-containing (meth)acrylate of the present invention represented by the general formula 0) are shown below. Note that R here represents a hydrogen atom or a methyl group, and d and e
represents an integer from 1 to 20.

As is known, two types of ring-opening reactions occur in monocyclic compounds such as R,0R11, and the ratios of these reactions vary depending on the type of cyclic compound, reaction conditions, and type of catalyst.

In the case of R,, R■, RO-CH-CH-OH and RO-CH-CH
-OHI+ R, OR1, R1, R,.

Two food reactions occur. Therefore, in the case of an addition reaction of n moles, the notation R1°ILtt R11R1° (here f+g=n) R,OR1° is used to represent all.

SaR3 Akira Akira 2 ♂H2 SaH Shin pt. Akira! CH.

CH,=C-C00CH,CH,0- Ht CH.

(Here, f+g=e) [Effects of the Invention] The hydroxyl group-containing (meth)acrylate having the novel structure of the present invention has hydroxyl groups and (meth)acrylates in the molecule.
Since it has three types of reactive groups, an acryloyl group and an alkenyl group, these three types of functional groups can be used as desired for a wide range of applications.

For example, a (meth)acryloyl group can be polymerized to form a (co)polymer having a hydroxyl group and an alkenyl group. Furthermore, by reacting the hydroxyl group with a compound having a reactive group such as an isocyanate group or an epoxy group, a vinyl compound having a (meth)acryloyl group and an alkenyl group can be produced, and these can be made into a homopolymer or Alternatively, it can be copolymerized with other vinyl monomers. Furthermore, alkenyl groups can be reacted with compounds that are reactive with alkenyl groups, such as thiols.

Therefore, the hydroxyl group-containing (meth)acrylate with the novel structure of the present invention can be used in paints, adhesives, inks, and textile modifiers by utilizing the reaction of the three types of reactive groups in the molecule. It can be used for a wide range of applications such as quality materials, radiation-curable resins, sealants, and surface modification materials.

〔Example〕

Next, the present invention will be explained with reference to examples, but the present invention is not limited to these examples.

In the examples, the reaction rates of alkenyl glycidyl ethers (a) and cyclic compounds (b) were measured by gas chromatography.

In addition, the structure of the reaction product is IR%H-NMRlxsC-
Confirmed by NMR and hydroxyl value. Furthermore, parts in the examples are parts by weight.

Example 1 2-Hydroxyethyl acrylate 139 as 1-hydroxy(meth)acrylate was placed in a reaction vessel equipped with a thermometer, stirrer, dropping funnel, gas inlet tube and manometer.
part (1,2 mol), 0 hydroquinone as a polymerization inhibitor
．． 3 parts, 2.7 parts of tungstophosphoric acid as a catalyst, and 410 parts of allyl glycidyl ether (3,6 -el) was added dropwise over a period of 4 hours. During the dropwise addition of allyl glycidyl ether, the reaction vessel was cooled down to an internal temperature of 30 to 4
I kept 0'CK. After the completion of dropping, continue stirring for 1 hour at 40°C.
The reaction was completed by aging at ℃. The reaction rate of allyl glycidyl ether was measured to be 99.8. Next, 11 parts of powdered magnesium silicate as an adsorbent was added, and the reaction product 539 was stirred at 40°C for 30 minutes.
(yield 98.1%). The diester content in the reaction product was 0.11-, and no 1-glycol was detected. As a result of hydroxyl value and NMR analysis, it was found that the average number of allyl glycidyl ethers added was 3, indicating that the acrylate had a hydroxyl group having the following structure.

CH,=CHC00CH,CH,0(Cl-1,CHO
(Hl τ mountain CH, CH=CH.

The infrared absorption spectrum is shown in FIG. 1, the H-NMR spectrum is shown in FIG. 2, and the 13C-NMR spectrum is shown in FIG. 3.

Example 2 In a reaction vessel similar to Example 1, 2-hydroxyethyl acrylate 17 was added as hydroxy(meth)acrylate.
4 parts (1.5 moles), 0.26 parts of hydroquinone monomethyl ether as a polymerization inhibitor, and 2.6 parts of tungstophosphoric acid as a catalyst, and while maintaining the internal temperature at 30 to 40°C, 171 parts of allyl glycidyl ether ( 1.5 mol) was added dropwise over 1 hour. After the dropwise addition was completed, the mixture was further aged at 40° C. for 1.5 hours.

The conversion rate of allyl glycidyl ether was 99.8%. Next, 174 parts (3.0 mol) of propylene oxide was added dropwise at 30 to 40°C over 2.5 hours, and the mixture was further aged at 40°C for 2 hours to complete the reaction. The propylene oxide reaction rate was 99.6%.

After adding 11 parts of powdered magnesium silicate, the mixture was purified by pressure filtration to obtain 511 parts of a reaction product (yield: 98.5%) as a colorless transparent liquid. The obtained reaction product had a hydroxyl value of 159, an acid value of 0.13, and a color number (APHA) of 30. No glycol was detected at a diester content of 0.12%. As a result of analysis by hydroxyl value and NMR, the average number of allyl glycidyl ether and propylene oxide added was 3, and it was found to be a hydroxyl group-containing acrylate having the following structure.

CH.

Akira CH.

The infrared absorption spectrum is shown in Figure 4, the H-NMR spectrum is shown in Figure 5, and the C-NMR spectrum is shown in Figure 6.

Example 3 In a reaction vessel similar to Example 1, 116 parts of 2-hydroxyethyl acrylate (1 mo/I/), 0.23 parts of hydroquinone monomethyl ether, and 2.3 parts of tungstophosphoric acid were added.
228 parts (2 mol) of allyl glycidyl ether and 114 parts (1 mol) of ε-
After dropping the mixture with caprolactone over 3 hours,
The reaction was completed by holding at 0° C. for 2 hours. The reaction rates of allyl glycidyl ether and ε-caprolactone were 99.8% and 98.6%, respectively. After adding 13.8 parts of magnesium silicate, it was purified by pressure filtration,
Hydroxyl value 121, acid value 0.09, color number (APHA) 3
448 parts (yield 97.8%) of a reaction product of 0.0 were obtained. The diester content in the reaction product was 0.11%, and no glycol was detected. Hydroxyl value and NM
As a result of analysis by R, allyl glycidyl ether and ε
- The average number of caprolactone additions was 3, and it was found that this was a hydroxyl group-containing acrylate having the following structure.

CH,=CHC00CH,CH,O- ■ CH.

CH Sophistry CH.

Example 4 In a reaction vessel similar to Example 1, 29 parts (0.25 mol) of 2-hydroxyethyl acrylate, 90 parts (1.25 mol) of tetrahydrofuran, 0.27 parts of hydroquinone monomethyl ether, and 11 parts of tungstosilicic acid were added. Preparation, at 25-35°C, allyl glycidyl ether 428
(3.75 mol) was added dropwise over a period of 6 hours, and the reaction was completed by further holding at 45° C.K. for 2 hours. The reaction rates of tetrahydrofuran and allyl glycidyl ether were 91.0% and 98.9%, respectively.

After completion of the reaction, the unreacted raw materials were removed by holding at 40°C for 30 minutes under a pressure of 20 mmHH, and then 39 parts of magnesium silicate was added and purified by pressure filtration to obtain a hydroxyl value of 2.
6,2, an acid value of 0.10, and a color number (APHA) of 30, 510 parts (yield: 93.2 parts) of a reaction product were obtained.

The diester content in the reaction product is 0.114,
No glycol was detected. Hydroxyl value and NMT
As a result of analysis by L, the average addition number of tetrahydrofuran and allyl glycidyl ether was 19.5.
It was found to be a hydroxyl group-containing acrylate with the following structure.

CH,=CHC00CH,CH,O- CH.

CH CH.

Example 5 In a reaction vessel similar to Example 1, 13 o parts (1 mol) of 2-hydroxyethyl acrylate, 0.14 parts of hydroquinone monomethyl ether, and 2.83 parts of tungstophosphoric acid were added.
342 parts (3 moles) of allyl glycidyl ether were added dropwise at 30 to 40'C over a period of 3 hours, and the reaction was further maintained at 40'C for 3 hours to complete the reaction.

The reaction rate of allyl glycidyl ether was 99.8%. Next, 15 parts of powdered basic magnesium aluminum hydroxy carbonate hydrate as an adsorbent was added, stirred at 60°C for 30 minutes, and purified by pressure filtration, with a hydroxyl value of 118 and an acid value of o. ,12,
Colorless transparent liquid reaction product 46 with color number (APHA) 30
3 parts (yield 98.1 t) were obtained. The diester content in the reaction product was 0.12%, and no glycol was detected.

As a result of hydroxyl value and NMRK analysis, it was found that the average number of allyl glycidyl ethers added was 3, and it was found to be a hydroxyl group-containing acrylate having the following structure.

Example 6 Into the same reaction vessel as in Example 1, 195 parts (1.5 mol) of 2-hydroxyethyl methacrylate, 0.16 part of hydroquinone monomethyl ether, and 2 parts of 117 dust silicic acid were added.
．． 15 parts of allyl glycidyl ether were added dropwise at 50'CK over a period of 2 hours, and the reaction was further maintained at 40'C for 1 hour to complete the reaction. The conversion rate of allyl glycidyl ether was 99.7%. 15 parts of powdered basic magnesium aluminum hydroxy carbonate hydrate, which is an adsorbent, was added to the mixture, stirred at 60°C for 30 minutes, and purified by pressure filtration to obtain a hydroxyl value of 155% and an acid value of 0. .10°Colorless transparent liquid reaction product with color number (APHA) 10 530
(yield 98.7%). The diester content in the reaction product was 0.10 S, and no glycol was detected. As a result of hydroxyl value and NMR analysis, it was found that the average number of allyl glycidyl ethers added was 2, and it was found to be a hydroxyl group-containing methacrylate having the following structure.

CH.

RoHl CH SaH8 Incidentally, the infrared absorption spectrum is shown in FIG.

Reference Example 1 Into the same reaction vessel as in Example 1, 139 parts (1.2 moles) of 2-hydroxyethyl acrylate and 0% of hydroquinone were added.
．． 3 parts, 3 parts of tungstophosphoric acid, and heated to 30-40°C.
468 parts (3.6 mol) of n-butyl glycidyl ether was added dropwise over 4 hours at 40°C.
The reaction was completed after a period of time. The reaction rate of n-butyl glycidyl ether was 99.7%. Next, 11 parts of powdered magnesium silicate, which is an adsorbent, was added and the mixture was heated to 40°C.
After stirring for 30 minutes, purification was performed by pressure filtration to obtain 595 parts of a reaction product (yield: 98.0%) as a colorless transparent liquid with a hydroxyl value of 109, an acid value of 0.53, and a color number (APHA) of 30.
I got it. The diester content in the reaction product was 0.10%, and no glycol was detected.

As a result of analysis by hydroxyl value and NMR, it was found that the average number of n-butyl glycidyl ethers added was 3, indicating that it was a hydroxyl group-containing acrylate having the following structure.

C4H.

Example 7 56 parts of the hydroxyl group-containing acrylate obtained in Example 1, 44 parts of pentaerythritol tetra(3-mercaptopropionate) and 3 parts of benzyl dimethyl ketal (manufactured by Ciba Geigy, Irgacure 651) were added,
A resin composition was prepared. The obtained resin composition was applied to a thickness of 15 μm on a steel plate panel, and irradiated with a high-pressure mercury lamp of 80 W/crrL from a distance of 10 parts ML while moving the panel at a conveyor speed of 6 m/min. However,
A tack-free cured coating was obtained with one irradiation. When we examined the performance of the resulting cured coating, we found that the pencil hardness was 3H.
The adhesion was 100/100.

The performance of the cured coating film was measured by the following method.

Pencil hardness: JIS K 5400 method Adhesion: Use a cutter knife on the coating for 10s+ at 1H intervals
100 goblets were cut in the range of s + x 10 inches, and after applying pressure to the tape, it was peeled off vigorously, and the peeling state of the goblins was observed and expressed as 100 - (number of goblins peeled off)/100.

Comparative Example 1 56 parts of the hydroxyl group-containing acrylate obtained in Reference Example 1, 44 parts of pentaerythritol tetra(3-mercaptopropionate) and 3 parts of benzyl dimethyl ketal (manufactured by Ciba Geigy, Irgacure 651) were added,
A comparative resin composition was prepared. Using the obtained comparative resin composition, the curability of the coating film was examined in the same manner as in Example 7, and it was found that 8 times of irradiation was required to obtain a tack-free cured coating film. Furthermore, when the performance of the cured coating film obtained in 1 was examined, the pencil hardness was 4B and the adhesion was 15/100.

The results obtained in Example 7 and Comparative Example 1 show that the hydroxyl group-containing (meth)acrylate of the present invention reacts with thiols to form an excellent cured coating film.

[Brief explanation of drawings]

FIG. 1 is an infrared absorption spectrum diagram of the hydroxyl group-containing acrylate obtained in Example 1, FIG. 2 is an H-NMR spectrum diagram of the hydroxyl group-containing acrylate obtained in Example 1, and FIG. FIG. 4 is an infrared absorption spectrum diagram of the hydroxyl group-containing acrylate obtained in Example 2, and FIG. 5 is an infrared absorption spectrum diagram of the hydroxyl group-containing acrylate obtained in Example 1. H-NMR of the hydroxyl group-containing acrylate obtained in
Figure 6 is a 1''C-NMR spectrum of the hydroxyl group-containing acrylate obtained in Example 2, and Figure 7 is an infrared absorption spectrum of the hydroxyl group-containing methacrylate obtained in Example 6. It is a diagram.

Claims (1)

[Claims] 1. General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (I) [However, in the formula, R is a hydrogen atom or a methyl group, and Z
represents a divalent organic group having 2 to 8 carbon atoms, (A) is a ring-opening group of alkenyl glycidyl ethers represented by the following general formula (II), and (B) is a ring-opening group of alkenyl glycidyl ethers represented by the following general formula (II). represents a ring-opening group of a cyclic compound excluding the alkenyl glycidyl ethers shown, l is an integer of 1 to 20, m is 0 or 1 to
It represents an integer of 20, and the arrangement of the ring-opening groups of the alkenyl glycidyl ethers or cyclic compounds represented by (A) and (B) is arbitrary. ] Hydroxyl group-containing (meth)acrylate. ▲Contains mathematical formulas, chemical formulas, tables, etc.▼(II) [In the formula, R^1 is a hydrogen atom or a (halo-substituted) hydrocarbon group having 20 or less carbon atoms, and R^2 is a hydrogen atom with a carbon number of 20 or less.
The following alkenyl groups. [2] The hydroxyl group-containing (meth)acrylate according to claim 1, wherein the alkenyl glycidyl ether is allyl glycidyl ether. 3. A patent claim in which the cyclic compound other than alkenyl glycidyl ethers is one or more compounds selected from the group consisting of alkylene oxide, ε-caprolactones, tetrahydrofuran, alkyl glycidyl ether, aryl glycidyl ether, and epihalohydrin. A hydroxyl group-containing (meth)acrylate according to Item 1 or 2 of the scope.