JPH04178454A - Ultraviolet-curing resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject ultraviolet-curing resin composition excellent in moldability and capable of providing an ultraviolet-cured molding having adhesion to metals, flexibility and heat resistance by blending a low-melting polyester resin with a specified epoxy resin and a photopolymerization initiator. CONSTITUTION:With (A) 100 pts.wt. low melting polyester resin, preferably synthesized from an acid component composed of a mixture of terephthalic acid and isophthalic acid and a glycol component composed of ethylene glycol, etc., (B) 5-100 pts.wt. cationic-polymerizable compound mixture mainly composed of an epoxy resin (preferably bisphenol type resin, novolak type resin, etc.) having two or more oxirane rings in one molecule and arbitrarily containing a cationic-polymerizable vinyl compound, etc., and (C) a photopolymerization initiator (e.g. aromatic diazonium salt) capable of initiating a cationic polymerization by application of ultraviolet rays in an amount of 0.5-30 pts.wt. based on 100 pts.wt. (B) are blended, thus obtaining the objective ultraviolet-curing composition.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to an ultraviolet curable resin composition, and particularly to an ultraviolet curable composition comprising a polyester resin and an epoxy resin.

UV-curable molded products using the composition of the present invention include various heat-resistant films, tapes, carriers, coatings (paints, coating agents, etc.), coatings (electric wires, optical fibers, etc.), heat-resistant fibers,
It is useful as a molded product.

[Prior Art 1] Ultraviolet curable resin compositions comprising thermoplastic saturated polyester resins such as polyethylene terephthalate resins and epoxy resins are known. For example, JP-A-60-228527
The publication discloses an ultraviolet curable resin composition of polyethylene terephthalate resin and epoxy resin, and JP-A No. 2-12
No. 3137 describes a film of the above composition by the present inventors.

[Problem to be Solved by the Invention 1] However, when trying to actually obtain film products using these techniques, the processability of forming Ifa is poor, and
It is necessary to carry out the method under limited and special conditions as described in Japanese Patent No. 121822.

Even under these special conditions, it is very difficult to suppress the generation of gel (unwanted material) when attempting to carry out long-term continuous molding processing.

[Means for Solving the Problems] The present inventors have developed a method that is capable of long-term continuous molding processability, and
As a result of intensive research aimed at establishing a technology to provide products with good adhesion to metals, flexibility, and heat resistance, we discovered the following composition.

That is, the present invention includes 100 parts by weight of component IAI/low melting point polyester resin,
Component (Bl: cationic polymerizable compound whose main component is an epoxy resin having two or more oxirane rings in one molecule
5 to 100 parts by weight, and further contains 0.5 to 30 parts by weight per 100 parts by weight of component (C): a photopolymerization initiator that initiates cation weight parts by irradiation with ultraviolet rays. This is an ultraviolet curable resin composition.

[Detailed description of the invention] (1) Components Low melting point polyester tree F3fA+ The low melting point polyester resin used in the present invention is:

A polymer produced by condensation polymerization using dicarboxylic acid and its ester-forming derivatives as the acid component and glycol and its ester-forming derivatives as the alcohol component.
nB Co1oriIIIeter, abbreviated as DSC)
When heated at a temperature increase rate of 10°C/min, no melting point is observed, or even if it is observed, it is less than 160°C.

Such a polyester resin can be obtained by using, as a dicarboxylic acid component, a mixture of different dicarboxylic acids in which terephthalic acid is mixed with isophthalic acid, naphthalene dicarboxylic acid, or the like.

It can also be obtained by using a mixture of ethylene glycol and different glycols such as propylene glycol and polyethylene glycol as the glycol component for a single dicarboxylic acid or a mixture of different dicarboxylic acids.

The molecular weight of the polyester resin used in the present invention is 300
It is 0 or more, preferably 5000 or more.

The dicarboxylic acids of the acid component include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalene dicarboxylic acid, and aliphatic dicarboxylic acids such as succinic acid, adipic acid, and sepatic acid. Furthermore, oxycarboxylic acids such as hexahydroxyethoxybenzoic acid can also be used as the acid component.

As the glycol, ethylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, cyclohexane dimethylol, polyethylene glycol, polypropylene glycol, etc. can be used.

Preferred polyester resins include those in which the acid component is an aromatic dicarboxylic acid and the glycol component is (poly)alkylene glycol. Specifically, for example, a mixture of terephthalic acid and isophthalic acid is used as the acid component, and ethylene glycol is used as the glycol component. ,Propylene glycol,
Tetramethylene gelcol, polyethylene glycol,
It is polymerized from one or a mixture of two or more polypropylene glycols.

The composition of the present invention may contain other thermoplastic resins, such as polyethylene terephthalate, polybutylene terephthalate, polyarylate, polyamide, polyoxymethylene, polycarbonate, polyethylene, polypropylene, polystyrene, as long as the properties of the low-melting polyester are not lost. , styrene-butadiene copolymer, etc. can also be blended.

Cationic care Chemical formation (B) The cationic polymerizable compound blended as the Bl component in the ultraviolet curable resin composition of the present invention is mainly composed of an epoxy resin having two or more oxirane rings in one molecule. It is one kind or a mixture of two or more kinds of cationic polymerizable compounds,
As this epoxy resin, bisphenol type epoxy resin, novolak type epoxy resin, alicyclic epoxy resin, etc. are preferable.

Examples of such bisphenol-type epoxy resins include Epicote 828, Epicote 834, Epicote 836. Epicote 1001. Epicoat 1004, Ebiko)-1007 (manufactured by Yuka Shell Epoxy Co., Ltd.)
Product name), DER331, DER332, DER6
61, DER664, DER667 (trade names, manufactured by Dow Chemical Company), Aralgate 260, Araltite 280. Araldite 6071. Araldite 6084
, Araldite 6097 (manufactured by Ciba Geigy,
(trade name), and these may be used alone or in combination.

Examples of the novolac type epoxy resin include Epicote 152, Epicote 154 (trade name, manufactured by Yuka Shell Epoxy Co., Ltd.), Araldite EPN 1138.
Araldite EPN 1139, Araldite ECN
1235, Araldite ECN 1273, Araldite ECN 1280, Araldite ECN 1299
(The above are manufactured by Ciba Geigy, product name), DEN 4
31, DEN 438 (trade name, manufactured by Dow Chemical Company), etc., and these may be used alone or in combination.

As the alicyclic epoxy resin, for example, Ebiko 1 to 19
011. Epicoat +9113 (manufactured by Yuka Shell Epoxy Co., Ltd., trade name), Araldite CY 175, Araldite CY 177, Araldite CY 179, Araldite CY 184. Araldite CY 192
(hereinafter manufactured by Ciba Geigy, product name), ERL-
4221, ERL-4299゜Er1L-4234, U
VR-6100, UVR-6110, UVR-6200
(all trade names manufactured by Union Carbide), etc., and these may be used alone or in combination.

Other butadiene-based epoxy resins can also be used, and mixtures of the various epoxy resins mentioned above can also be used.

A monofunctional epoxy diluent may be used in the cationic polymerizable compound used in the present invention within a range that does not deteriorate the curing properties. Examples of such l-functional epoxy diluents include phenyl glycidyl ether and tert-butyl glycidyl ether.

Furthermore, it is also possible to use a cationic polymerizable vinyl compound mixed with the epoxy resin, and examples of such cationic polymerizable vinyl compounds include styrene, allylbenzene, triallyl isocyanate, triallylcyanate, vinyl ether, N -vinylcarbazole, N-vinylpyrrolidone, and the like.

Photopolymerization initiator fc) The photopolymerization initiator fcl, which is blended during the production of the heat-resistant polyethylene terephthalate film of the present invention, is a compound that liberates a Lewis acid catalyst that initiates the polymerization of a cationically polymerizable compound upon irradiation with ultraviolet rays. aromatic diazonium salt, aromatic halonium salt, group VB or group V
Examples include photosensitive aromatic onium salts of group Ib elements and iron-aromatic compounds.

Such an aromatic diazonium salt has the formula (I
): In the formula, R' and R2 are hydrogen atoms, alkyl groups, or alkoxy groups, and ■(3 is connected by a hydrogen atom, an aromatic group, an amide group, or an atom) M is a metal or metalloid, q represents a halogen atom, a is an integer of 1 to 6, and a
=(b-c) holds, C is an integer from 2 to 7 and is equal to the valence of M, and b represents an integer greater than C and less than or equal to 8.

Such compounds include, for example.

Examples include.

Further, the aromatic halonium salt has the general formula [R'l,
(R'),Xl,"1MQ,]-"-"
(III1 (in the formula, R4 is a monovalent aromatic organic group, R5 is a divalent aromatic organic group, X is, for example, I, B
r, a halogen atom such as CI, M is a metal or metalloid, Q is a halogen atom, and d is 0 or 2. e is 0
or 1, and (die) is equal to 2 or the valence of X, and g represents an integer greater than h and equal to or less than 8).

Further, as the photosensitive aromatic onium salt of group Vb element or group Vlb element, - formula (III) lfR6
), IR')jfllBlkY+, "[Q-L'"-"
fllll (wherein, R6 is a monovalent aromatic organic group, R7 is a monovalent aliphatic organic group selected from the group consisting of an alkyl group, a cycloalkyl group, and a substituted alkyl group, and R'' is an aliphatic organic group and A polyvalent organic group constituting a heterocyclic structure selected from aromatic organic groups, a group Vlb element of Yc′iS, Se, Te, or a group Vb element selected from N, P, As, Sb, and Bi. 1M represents a metal or metalloid, 0 represents a halogen atom, i is an integer of 0 to 4, j is an integer of D to 2, and is an integer of 0 to 2, and lDj
+k) is equal to the valence of Y, and when Y is in group Vl b, 3. When Y is in group vb, it is equal to 4, i=im-n
l holds true, and.

The number is an integer from 2 to 7 and is equal to the valence of M, where m represents an integer greater than n and less than or equal to 8. ).

Examples of onium salts of Group Vlb elements include the following.

Further, examples of onium salts of Group VB elements include the following.

In addition, examples of iron-aromatic compounds include C.I.

Examples include.

The amount of the cationically polymerizable compound + Bl added to 100 parts by weight of yKuratan low melting point polyester resin fA) is 5 to 1
00 parts by weight, preferably 10 to 80 parts by weight, more preferably 15 to 70 parts by weight. If the amount is more than 100 parts by weight, the resulting composition will have poor flexibility, and if it is less than 5 parts by weight, the heat resistance will be poor. The amount of agent 1cI is 10% of the cationically polymerizable compound.
0.5 to 50 parts by weight, preferably 1 to 0 parts by weight
The amount is 40 parts by weight, more preferably 2 to 30 parts by weight. If it is less than 0.5 parts by weight, the effect of ultraviolet irradiation will be small, and if it is added in excess of 50 parts by weight, the effect will remain constant even though the cost of the initiator will increase.

The composition of the present invention is prepared by first mixing the above-mentioned constituent components, low melting point polyester resin +A) and a cationic polymerizable compound (Bl).
are mixed by ordinary mixing means such as a Ripon blender, ■-blender, etc., and further generally by ordinary melt-kneading means,
The mixture is melted and kneaded for 1 to 10 minutes at a temperature higher than the softening point (or melting point) of each component using an 1-axis or 2-axis kneader to form pellets.

A photopolymerization initiator is usually added during the subsequent molding process to avoid decomposition of the photopolymerization initiator.

The obtained pellets and photopolymerization initiator + C) are molded into various films, tapes, sheets, fibers, molds, etc. using a conventional extruder, injection molding machine, blow molding machine, press molding machine, etc. Processed into molded products.

When a solvent that appropriately dissolves the composition of the present invention is present, the solution obtained by dissolving the constituent components (A), (B), and (C) in the solvent may be dissolved in an appropriate solvent. Various methods such as brush coating, roll coating, spray coating, dipping,
It is also possible to obtain a molded article by coating by a casting method or the like and then removing the solvent by evaporation.

The molded article obtained by each of the above methods is irradiated with ultraviolet rays at a temperature below the softening point (or melting point) of the non-grade polyester resin.

The irradiation time is 1 second or more and 100 seconds or less, preferably 60 seconds or less. Ultraviolet rays are generally 10 (1 to 5
00 am, preferably a wavelength of 200 to 4501 m.

The composition of the present invention is manufactured by irradiating ultraviolet rays by the method described above, but it is not necessarily limited to the method described above.

[Operation J] Since the composition of the present invention uses a specific polyester resin, the polyester is not crosslinked during molding of the resin composition, and therefore has excellent molding processability and can produce thick, homogeneous films, etc. can be molded.

[Example 1] The characteristics of the composition of the present invention will be specifically explained below with reference to Examples.

The measurement method for each measurement item in the examples is as follows.

(a) Using melting point DSC (manufactured by DuPont, 91O), sample amount 5
A sample prepared by rapidly cooling 280° C. into ice water was heated at a heating rate of 10° C./min, and the position of the rapid heating peak that appeared was taken as the melting temperature.

(b) Intrinsic viscosity Measured at 20°C using a mixed solution of phenol/tetrachloroethane = l/l.

(c) Soldering heat resistance 2klf high pressure mercury lamp (30w/cm ) at a distance of 20cm.

The ultraviolet irradiated film was irradiated for 15 seconds at 110°C.
It was immersed in a solder bath at 60°C and visually judged whether or not it melted.

(d) Manual folding test (c) Ultraviolet irradiation film was folded by hand at room temperature for 180°
The film was repeatedly bent by 30° and the number of bends required to break was expressed as the number of times it took to break.

(e) Copper foil adhesion Film and copper foil (200μs+) before UV irradiation.

After heating and pressing at 250° C. and 50 kg/ca+2, the pressure was increased and the material was cooled and laminated at 100 kg/csw2.

Next, after irradiating the adhesive resin surface with ultraviolet rays, the resin and copper foil were peeled off at a rate of 0III/min per mouth with a width of 10+u+ using an autograph, and the 180[deg.] tensile strength was expressed.

Examples 1-5, Comparative Examples 1-4 Polyester resin (a, 1 Manufactured by Kanebosha, PIFG-20.

Amorphous polyester resin obtained using terephthalic acid (80 mol% of the acid component) and isophthalic acid (20 mol%) as the acid component and ethylene glycol as the glycol component, intrinsic viscosity: 0, 65. Melting point: Not observed.

Epoxy resin (bl) Bisphenol A epoxy resin E828, manufactured by Yuka Shell Epoxy Co., Ltd. Molecular weight: 306. Epoxy equivalent: 103
゜ were blended in the proportions shown in Table 1 and mixed using a blender.
Cylinder temperature 2 with EX30 (manufactured by Japan Steel Works)
Melt and knead at 60°C and screw rotation speed of 20 rpm,
A beret as a molding material was obtained.

Next, triphenylsulfonium hexafluoroantimonate as a photopolymerization initiator (cl) was mixed in a blender at the ratio shown in Table 1 with respect to the molding material 1a+"b+) previously formed into a beret, and 30 On+s was added to the tip. T of
Using the two-shaft Mi machine equipped with a die, the rotation speed was 200 rpm at each cylinder temperature and residence time in the cylinder shown in Table 1.
The film was melt-extruded at a speed of 100 m and rapidly cooled using a roll to obtain a transparent unstretched film with a thickness of 200 μm.

The obtained film was evaluated according to the method described above. The results are shown in Table 1.

The Examples had better molding processability during film molding than the Comparative Examples, and the properties of the obtained films were good.

Example 6 A non-grade polyester resin tai1. was obtained using terephthalic acid (70 mol%) and isophthalic acid (30 mol%) as the acid components and ethylene glycol as the glycol component. PIFG-30 (manufactured by Kanebo Co., Ltd., intrinsic viscosity 0.
The experiment was conducted in the same manner as in Example 2, except that 62, melting point, not observed) was used.

The results are shown in Table 1. Similar to Example 2, the film had excellent film moldability and film properties.

Comparative Example 5 Polyethylene terephthalate resin (a3) obtained using terephthalic acid as the acid component and ethylene glycol as the glycol component, PBK-1 (manufactured by Kanebo Co., Ltd., intrinsic viscosity: 0.70, melting point = 253 ° C.) was used. Except for the above, the same experiment as in Example 2 was conducted.

The results are shown in Table 1. It can be seen that the moldability of the Kurabe film in Example 2 and the adhesion of the obtained film to copper foil were inferior.

Comparative example 6 Terephthalic acid (88 mol%) as an acid component.

Uses PZFG-12 (manufactured by Kanebo Co., Ltd., intrinsic viscosity: 0.62, melting point: 210°C), a non-grade polyester resin (a4) obtained by using isophthalic acid (12 mol%) and ethylene glycol as the glycol component. The results are shown in Table 1. It can be seen that the moldability of the Kurabe film in Example 2 and the adhesion of the obtained film to copper foil were inferior.

Example 7 Vylon 30P as non-quality polyester resin (a5)
(Manufactured by Toyobo, intrinsic viscosity: 1.0, melting point: 130°C)
The same experiment as in Example 2 was conducted except that .

The results are shown in Table 1. Similar to Example 2, excellent film molding processability and film properties were exhibited.

Example 8 An experiment similar to Example 2 was conducted except that alicyclic epoxy resin UVR-6100 (manufactured by Union Carbide Co., Ltd., epoxy equivalent: 130 to 140) was used as the cationic polymerization compound (b2).

The results are shown in Table 1, and it can be seen that the film has excellent film moldability and film properties similar to Example 2.

Example 9 As a photopolymerization initiator (c2) (η6-benzene l (n
The same experiment as in Example 2 was carried out except that iron ('-cyclopentagel) iron-hexafluorophosphate was used.

The results are shown in Table 1. It can be seen that, like Example 2, it has excellent film moldability and film properties.

Example IO1 Comparative Example 7 10 g of the same blended composition as in Example 2 and Comparative Example 6 was melted in 100 g of hexafluoroisopropanol as a solvent,
Use a bar coater to coat a 20 hm thick copper foil with a thickness of 20 hm.
It was coated to a thickness of g+n. After being left at room temperature for 12 hours to completely evaporate the solvent, it was irradiated with ultraviolet light under the same conditions as in Example 2 and evaluated.

The results are shown in Table 1. Similar to Example 2 and Comparative Example 6, it can be seen that the composition according to the present invention has excellent film properties.

[Effects of the Invention] The ultraviolet curable resin composition of the present invention has excellent moldability by combining a low-melting point polyester resin, a specific epoxy resin, and a photopolymerization initiator, and has excellent moldability and compatibility with metals. It is a composition that provides an ultraviolet-curable molded article having adhesion, flexibility, and heat resistance, and the products obtained using the composition of the present invention include various heat-resistant films, tapes, carriers, coatings (paints, coatings, etc.). agent, etc.), wave diaphragm (electric wire,
It is useful as optical fibers, etc.), heat-resistant fibers, and molded products.

Claims (1)

[Claims] (1) Component (A): 100 parts by weight of low melting point polyester resin Component (B): 5 to 10 cationic polymerizable compounds whose main component is an epoxy resin having two or more oxirane rings in one molecule
0 parts by weight, and further contains component (C): a photopolymerization initiator that initiates cationic polymerization upon irradiation with ultraviolet rays, from 0.5 to 30 parts by weight per 100 parts by weight of component (B). Curable resin composition.