JP2003002919A - Novel di(meth)acrylate and curable composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel (meth)acrylate that gives cured products having excellent adhesion to a variety of resins and showing a low water absorption, and provide a curable composition containing the same. SOLUTION: The di(meth)acrylate is represented by the following formula (1) (wherein R1 is a H atom or methyl group) and a curable resin composition containing the same.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel di (meta).
Acrylate, which relates to a curable composition containing the acrylate, the di (meth) acrylate and the curable composition of the present invention can be used in various applications such as paints, inks, resists and molding materials. It can be prized in the technical field.

[0002]

2. Description of the Related Art In recent years, a printed circuit board on which electronic parts are mounted is often used in electric appliances and electronic devices, but the surface of the printed circuit board may be condensed depending on the place and time of use. , Waterproof treatment is required. As one of the means for waterproofing, a waterproof paint in which a polymer is dissolved in a solvent is used. However, since the conventional waterproof paint uses a solvent, it takes time to dry the coating film. In addition, there is a problem of working environment, and there is a demand for a solvent-free, quick-curing waterproof coating.

In the field of electronic materials, resin materials are often used as a laminated film in which several resin layers are laminated. Therefore, development of pressure-sensitive adhesives and adhesives for laminating the respective resin layers is required. With these adhesives / adhesives, not only the cured product is transparent, but also the adhesion to various resins is good so that the transparency of the laminated film is not impaired, and the dimensional change of the cured product is small. It is important that the water absorption rate is low.

To solve the above-mentioned problems, (meta)
There is an active energy ray-curable composition containing acrylate as a main component, but even if a conventionally known (meth) acrylate is combined, there is a limit to solving the above problems.

The inventors of the present invention have conducted earnest studies to find a novel (meth) acrylate having a cured product obtained which is excellent in adhesion to various resins and has a low water absorption rate, and a composition containing the same.

[0006]

Means for Solving the Problems As a result of various investigations for solving the above problems, the present inventors have found that di (meth) acrylate having a specific structure can be obtained as a cured product of various resins. It has been found that the adhesiveness is excellent and the water absorption is low, and the present invention has been completed. Hereinafter, the present invention will be described in detail. In the present specification, acrylate or methacrylate is referred to as (meth) acrylate, acrylic acid or methacrylic acid is referred to as (meth) acrylic acid, and acryloyl group or methacryloyl group is referred to as (meth) acryloyl group.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION 1. Di (meta) represented by formula (1)
Acrylate The novel di (meth) acrylate of the present invention is a di (meth) acrylate having a terephthalic acid residue and a butylene group represented by the following formula (1) [hereinafter referred to as a novel di (meth) acrylate].

[0008]

[Chemical 2]

[In the formula (1), R ₁ is a hydrogen atom or a methyl group. ] The novel di (meth) acrylate of the present invention has a butylene group. If this is different from a butylene group, for example, one having an ethylene group or one having a hexyl group, the water absorption of the obtained cured product will be reduced.

The novel di (meth) acrylate can be produced by various methods, and the method of producing it by esterification of n-hydroxybutyl (meth) acrylate with terephthalic acid or terephthalic acid chloride is preferred. However, since terephthalic acid has extremely low solubility in various organic solvents, a method using terephthalic acid chloride is preferable.

The method of esterification is as follows:
A method performed in the presence of a radical polymerization inhibitor is preferred. In the esterification reaction, n-hydroxybutyl (meth) acrylate was placed in a reaction vessel in advance,
Terephthalic acid chloride may be added dropwise, or conversely, terephthalic acid chloride may be placed in a reaction vessel in advance and n-hydroxybutyl (meth) acrylate may be added dropwise. Usually, the molar ratio of n-hydroxybutyl (meth) acrylate and terephthalic acid chloride is preferably n-hydroxybutyl (meth) acrylate / terephthalic acid chloride = 2/1 or more. When the proportion of n-hydroxybutyl (meth) acrylate used is small, by-products other than the desired di (meth) acrylate are likely to be produced and the yield is reduced. Conversely, n-
If the proportion of hydroxybutyl (meth) acrylate is too high, the radical polymerizable component in the reaction solution may increase, which may cause a polymerization reaction during the reaction. Also, it is not preferable from the economical point of view. Therefore, it is preferable to use it in an amount not more than 3 times that of terephthaloyl chloride.

The esterification reaction is preferably carried out in an organic solvent. As the organic solvent, an ether solvent such as diethyl ether, tetrahydrofuran and dioxane,
Aromatic hydrocarbon solvents such as benzene, toluene and xylene, and non-reactive organic solvents such as aliphatic hydrocarbon solvents such as n-heptane, cyclohexane and n-hexane are mixed singly or in combination of two or more. To use. The amount of the organic solvent used is not particularly limited, but is usually 10 mass times or less, and preferably 0.5 to 10 times, the total weight of n-hydroxybutyl (meth) acrylate and terephthalic acid chloride. It is 5 times or less by mass.

The radical polymerization inhibitor is not particularly limited as long as it is a compound capable of trapping radicals, but preferred examples are hydroquinone, methoxyhydroquinone, ethoxyhydroquinone, methylhydroquinone,
Conventional conventionally known radical polymerization inhibitors such as phenothiazine, t-butylcatechol and hypophosphorous acid can be used. These radical polymerization inhibitors may be used alone or in combination of two or more. Usually, it is preferably used in the reaction solution in the range of 10 to 10,000 ppm, more preferably 100 to 5000 ppm.

Further, in order to supplement hydrogen chloride generated in the reaction, it is preferable to add tertiary amines such as trimethylamine and triethylamine. These tertiary amines may be used alone or in combination of two or more,
Usually, one having an appropriate boiling point is selected in consideration of the solubility in the organic solvent used in the reaction and the reaction temperature, and one type is used. These amines may be put in the reaction vessel in advance before the reaction, or may be continuously dropped into the reaction vessel.

In the present invention, the esterification reaction is carried out usually in the range of 0 to 150 ° C, preferably room temperature to 120 ° C. The reaction is usually performed under normal pressure. The reaction time may be appropriately set according to the reaction conditions, and is usually in the range of 1 to 20 hours.

After completion of the esterification reaction, water is added to the obtained reaction mixture to dissolve the salt of hydrogen chloride and amine, which is precipitated by the reaction. An extraction solvent such as ethyl acetate or methylene chloride is added to this reaction solution to extract (meth) acrylate. Usually, an instrument such as a separating funnel is used for this operation, the organic layer and the aqueous layer are separated, and the organic solvent is distilled off from the obtained organic layer under reduced pressure to recover the (meth) acrylate. You can

2. Radical Polymerizable Monomer Although the novel di (meth) acrylate of the present invention can be used alone, the novel di (meth) acrylate is used for the purpose of improving the adhesiveness with a resin or adjusting Tg. It is also possible to use together radically polymerizable monomers other than acrylate. As the radical-polymerizable monomer, various compounds having one (meth) acryloyl group [hereinafter referred to as monofunctional (meth) acrylate], compounds having two or more (meth) acryloyl groups [hereinafter polyfunctional (meth)] Acrylate], and styrene derivatives such as styrene and divinylbenzene, and the like, and any of these can be used in any proportion depending on the purpose of use and desired physical properties.

As the monofunctional (meth) acrylate, phenol ethylene oxide modified (meth) acrylate, paracumylphenol ethylene oxide modified (meth) acrylate, nonylphenol ethylene oxide modified (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate. And high-boiling point (meth) acrylates such as isobornyl acrylate. In addition to these, low molecular weight and low boiling point (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and butyl (meth) acrylate can also be used.

As the polyfunctional (meth) acrylate, bisphenol F ethylene oxide-modified di (meth) acrylate, bisphenol A ethylene oxide-modified di (meth) acrylate, bisphenol Z ethylene oxide-modified di (meth) acrylate, isocyanuric acid ethylene oxide-modified Di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, pentaerythritol di (meth) acrylate monostearate,
2 such as polyethylene glycol di (meth) acrylate and polypropylene glycol di (meth) acrylate
(Meth) acrylate having 1 (meth) acryloyl group, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane propylene oxide modified tri (meth) acrylate, isocyanuric acid ethylene oxide modified tri (Meth) acrylate having three (meth) acryloyl groups such as (meth) acrylate, trimethylolpropane propylene oxide-modified tri (meth) acrylate, and trimethylolpropane ethylene oxide-modified tri (meth) acrylate can be exemplified. . Other than these, (meth) acrylates having 4 or more (meth) acryloyl groups can also be used. Further, oligomers such as polyester (meth) acrylate, urethane (meth) acrylate and epoxy (meth) acrylate can also be used. Examples of the epoxy (meth) acrylate include (meth) acrylates of glycidyl ethers such as glycerin diglycidyl ether, trimethylolpropane triglycidyl ether and triglycidyl isocyanurate, and bisphenol A type epoxy resin, phenol novolac type epoxy resin and cresol novolac type epoxy resin. (Meth) acrylate of epoxy resin such as resin may be used.

3. Photopolymerization Initiator The novel di (meth) acrylate and curable composition of the present invention are cured by irradiation with active energy rays or heating. In the case of curing by irradiation with active energy rays, it is cured by irradiation with electron beams, visible rays, ultraviolet rays, etc., but it is possible to use an inexpensive device and obtain a cured product with a large film thickness. A light ray or ultraviolet ray curable type is preferable. When the composition is a visible light or ultraviolet ray curable composition, a photopolymerization initiator is added to the composition. When the composition is an electron beam curable composition, it is not always necessary to add a photopolymerization initiator.

Specific examples of the photopolymerization initiator include benzoin such as benzoin, benzoin methyl ether and benzoin propyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, Acetophenones such as 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one and N, N-dimethylaminoacetophenone; Anthraquinones such as 2-methylanthraquinone, 1-chloroanthraquinone and 2-amylanthraquinone; 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,
Thioxanthones such as 4-diisopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone, methylbenzophenone, 4,4′-dichlorobenzophenone,
Benzophenones such as 4,4'-bisdiethylaminobenzophenone, Michler's ketone and 4-benzoyl-4'-methyldiphenyl sulfide; and 2,4,6
-Trimethylbenzoyldiphenylphosphine oxide and the like can be mentioned. The photopolymerization initiator may be used alone or in combination of two or more kinds. A photosensitizer can be used in combination with the photopolymerization initiator, if necessary. Examples of the photosensitizer include N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, triethylamine and triethanolamine. When the photopolymerization initiator is added, 0.05 to 12 parts by mass is added to 100 parts by mass of the new di (meth) acrylate or 100 parts by mass of the total amount of the new di (meth) acrylate and the radical-polymerizable monomer. It is preferably 0.1 to 2 parts by mass.

4. Thermal Polymerization Initiator When the novel di (meth) acrylate and curable composition of the present invention are cured by heating, a thermal polymerization initiator is added. Various compounds can be used as the thermal polymerization initiator, and organic peroxides and azo initiators are preferable.
Specific examples of the organic peroxide include 1,1-bis (t-butylperoxy) 2-methylcyclohexane and 1,1-
Bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5 -Trimethylcyclohexane,
1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (4,4-di-butylperoxycyclohexyl) propane, 1,1-bis (t-butylperoxy) cyclododecane, t- Hexyl peroxyisopropyl monocarbonate, t-butyl peroxymaleic acid, t-butyl peroxy-3,5,5-trimethylhexanoate, t-butyl peroxylaurate,
2,5-Dimethyl-2,5-di (m-toluoyl peroxy) hexane, t-butyl peroxyisopropyl monocarbonate, t-butyl peroxy 2-ethylhexyl monocarbonate, t-hexyl peroxybenzoate, 2, 5-Dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate, 2,2-bis (t-butylperoxy) butane, t
-Butyl peroxybenzoate, n-butyl-4,4
-Bis (t-butylperoxy) valerate, di-t-
Butyl peroxyisophthalate, α, α′-bis (t
-Butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-di (t
-Butylperoxy) hexane, t-butylcumyl peroxide, di-t-butylperoxide, p-menthane hydroperoxide, 2,5-dimethyl-2,
5-di (t-butylperoxy) hexyne-3, diisopropylbenzene hydroperoxide, t-butyltrimethylsilyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl Examples thereof include hydroperoxide and t-butyl hydroperoxide. Specific examples of the azo compound include 1,1′-azobis (cyclohexane-1-carbonitrile), 2- (carbamoylazo) isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile. ,
Examples thereof include azodi-t-octane and azodi-t-butane. These may be used alone or in combination of two or more. Further, it is possible to make a redox reaction by combining an organic peroxide with a reducing agent,
Nitrogen-containing compounds such as dimethylaniline and metal-containing compounds such as cobalt naphthenate can cause coloring and are not usually used. However, it can also be used depending on the situation. As the amount of these thermal polymerization initiators used,
It is preferable not to exceed 10 parts by mass with respect to 100 parts by mass of the new di (meth) acrylate or 100 parts by mass of the total amount of the new di (meth) acrylate and the radical-polymerizable monomer. When the thermal polymerization initiator is used alone, it may be carried out according to the conventional means of ordinary radical thermal polymerization,
In some cases, it may be used in combination with a photopolymerization initiator and, after photocuring, heat curing may be performed for the purpose of further improving the reaction rate.

5. Method of Use The novel di (meth) acrylate of the present invention can be used alone as a photo-radical-polymerizable monomer or a heat-radical-polymerizable monomer, or can be used in combination with a radical-polymerizable monomer or other components. it can.
In addition to the above components, an antifoaming agent, a leveling agent, an inorganic filler, an organic filler, a light stabilizer and the like can be blended, if necessary.

The novel di (meth) acrylate and curable composition of the present invention can be used for various purposes, and examples thereof include adhesives for resin films, paints, inks, resists and molding materials. In particular, the novel di (meth) acrylate and curable composition of the present invention are particularly useful as an adhesive for laminated films due to the physical properties of the cured product.

[0025]

EXAMPLES The present invention will be described more specifically below with reference to Examples and Comparative Examples. In the following, "parts" means parts by mass.

○ Example 1 [Production of novel diacrylate] * Method of sequentially adding terephthaloyl chloride In a 1 L flask, 250 g dioxane, triethyl
Min 54.83 g (0.5419 mol), hydroxy
Butyl acrylate 142.03g (0.9851mo
l) and the polymerization inhibitor Q-1301 [Wako Pure Chemical Industries, Ltd.
Manufacture, the same as below] Add 0.027 g (50 ppm)
Heated and refluxed. After starting reflux, terephthalic acid chloride 1
00g (0.4926mol) is divided into 10 parts, 15 minutes
It was added from a branch pipe at a distance. After adding acid chloride
And refluxed for another 2 hours. After 2 hours,
No white smoke was observed, so the reaction was stopped. Anti
After cooling the reaction solution to 60 ° C, add 300 g of water and add
After the monium salt is completely dissolved in water, ethyl acetate 30
The reaction was extracted with 0 g. In addition, add 300 g of vinegar to the water layer.
It was extracted with ethyl acidate. The obtained organic layer is mixed with 10% sulfuric acid 25
Wash 2 times with 0 g, then 5% NaHCO ₃200 g
It was washed with × 2. The organic layer is MgSO_FourAfter drying with a pressure filter
Excessive solvent removal gave 141.17 g of diacrylate.
(Yield 68.5%). Before removing the solvent, TLC (hexane
/ Ethyl acetate = 5/5), Rf: 0.7
It was 0. As a result of analyzing the obtained reaction product,
It was confirmed that crelate was generated. Analysis results
It is shown below.

-Analysis result 1) Melting point: high viscosity liquid clouded at room temperature 2) Elemental analysis (%) Calculated value: C: 63.15; H: 6.26; O: 30.59 Measured value: C: 64 .29; H: 5.93; O: 29.76 3) ¹ H NMR spectrum (270 MHz, measuring solvent CDCl ₃ ) The structural formula of the obtained acrylate is shown in formula (2), and a to h are assigned to each proton. Numbered. The attribution is as shown in Table 1.

[0028]

[Chemical 3]

[0029]

[Table 1]

Example 2 [Production of novel diacrylate] * Method of dropping hydroxybutyl acrylate / triethylamine into a 1 L flask, dioxane 200 g, terephthalic acid chloride 100 g (0.4926 mol), Q-130
1; 0.02 g (50 ppm) was added and heated to 80 ° C. The solution was not completely uniform, and terephthaloyl chloride was dispersed. Then triethylamine 5
A mixture of 4.83 g (0.5419 mol) and 142.03 g (0.9851 mol) of hydroxybutyl acrylate was charged over 3 hours. A large amount of ammonium salt and hydrogen chloride were produced during charging, but the internal temperature did not rise particularly. After the completion of charging, the bath temperature was raised and refluxed for 2 hours. After 2 hours, no white smoke of hydrogen chloride was observed, so the reaction was stopped. After cooling to 60 ° C., 200 g of water was added to completely dissolve the ammonium salt. An attempt was made to extract the reaction product with 250 g of ethyl acetate, but it was not separated, so 10% H ₂ SO ₄ 250
It was washed with g × 2 and the organic layer was collected. Then 5% NaH
It was washed with 200 g of CO ₃ × 2. The organic layer was dried over MgSO ₄ , filtered under pressure and desolvated to obtain 178.75 g of diacrylate (yield 86.7%). Before removing the solvent,
When LC (hexane / ethyl acetate = 5/5) was examined, Rf was 0.70, which was the same as that obtained in Example 1.

Examples 3 and 4 (Production of UV-curable composition) Each component shown in Table 2 was stirred and mixed according to a conventional method, and the composition was left for 15 minutes in a dryer kept at 80 ° C. Thus, the photopolymerization initiator was dissolved to produce an ultraviolet curable composition. Using a bar coater, apply the composition to a thickness of 5 on a polymethylmethacrylate (PMMA) plate or a glass plate.
Coating at 0 μm, conveyor speed 5 m / min, output 1
Ultraviolet irradiation was performed 10 times with a 60 W / cm high pressure mercury lamp under the condition of 0.8 J / cm ² . The obtained cured product was evaluated according to the following method. The results are shown in Table 2.
Shown in.

Evaluation 1) As a cross-cut test base material, a polymethylmethacrylate plate (hereinafter referred to as PMM)
(Hereinafter referred to as A plate), the cured product obtained on the PMMA plate was cooled, and then a cross-cut test was conducted according to JIS K5400. A cutter guide having a clearance of 1 mm was used, and evaluation was performed with 100 meshes of 1 mm × 1 mm. The evaluation results were evaluated by points according to the evaluation score table of the cross cut test.

2) Water absorption rate 5 cm of a resin sheet obtained by photo-curing on a glass plate.
It was cut into 5 cm and used as a test piece. The test piece was heated in nitrogen at 210 ° C. for 1 hour to completely dry the cured product, and then allowed to cool in a desiccator, and the test piece was weighed (W1). Then, the test piece was immersed in distilled water at 80 ° C. for 20 hours, taken out, and then water on the surface of the test piece was wiped off and weighed (W2), and the water absorption rate was calculated from the following formula.

[0034]

[Formula 1] Water absorption rate (%) = 100 × (W2-W1) / W1

○ Examples 5 and 6 (Production of thermosetting composition) After stirring and mixing the components shown in Table 2 at room temperature, 80 ° C
Bubbles contained in the obtained composition were removed over 15 minutes in a dryer maintained at 0.degree. C. to produce a thermosetting composition. The obtained composition was applied on a PMMA plate or a glass plate with a thickness of 50 μm using a bar coater, and then at 150 ° C.
Heat curing was carried out for 3 hours in the dryer. The obtained cured product was evaluated in the same manner as in Examples 3-4. The results are shown in Table 2.

[0036]

[Table 2]

The abbreviations in Table 2 have the following meanings. 1) Diacrylate obtained in Example 1 2) M-203: Aronix M-2 manufactured by Toagosei Co., Ltd.
03, tricyclodecane dimethanol diacrylate 3) HCPK: 1-hydroxycyclohexyl phenyl ketone 4) BDMC: benzyl dimethyl ketal 5) PD: Perbutyl D produced by NOF CORPORATION D: Ditertiarybutyl peroxide

[0038]

[Table 3]

The abbreviations in Table 2 are the same as those in Table 1
Has the same meaning as. 1) HETDA: a diacrylate represented by the following formula (3).

[0040]

[Chemical 4]

2) M-208: Aronix M-208 manufactured by Toagosei Co., Ltd., bisphenol F ethylene oxide 4 mol modified diacrylate 3) M-245: Aronix M-2 manufactured by Toagosei Co., Ltd.
45, polyethylene glycol diacrylate (ethylene oxide unit 9 mol)

From the results of the examples, according to the diacrylate and the curable composition of the present invention, the obtained cured product has excellent adhesion to the resin and low water absorption.

[0043]

INDUSTRIAL APPLICABILITY The novel di (meth) acrylate of the present invention can be used as a (meth) acrylate for active energy ray curing or heat curing, and the resulting cured product is excellent in adhesion and low water absorption. Therefore, the novel di (meth) acrylate or curable composition of the present invention can be applied to a paint field such as a waterproof paint for waterproof treatment of a printed circuit board that constitutes an electronic circuit of an electric appliance, which requires adhesiveness and low water absorption. First, it is extremely useful in various fields such as inks, resists, and molded products such as transparent acrylic plates.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4H006 AA01 AB46 BJ50                 4J100 AL03Q AL04Q AL08Q AL63Q                       AL66P AL66Q BA03Q BA08Q                       BA20P BA21Q BA39Q BA43Q                       BC43P CA01 CA04 JA01                       JA03 JA07 JA38

Claims (5)

[Claims] 1. A di (meth) acrylate represented by the following formula (1). [Chemical 1] [However, in the formula (1), R ₁ is a hydrogen atom or a methyl group. ] 2. A curable composition comprising the di (meth) acrylate according to claim 1 and a radical-polymerizable monomer other than this, if necessary. 3. The curable composition according to claim 2, wherein the radically polymerizable monomer is (meth) acrylate. 4. The curable composition according to claim 2, further comprising a photopolymerization initiator. 5. The curable composition according to claim 2, further comprising a thermal polymerization initiator.