JPH0224854B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a cationically polymerized energy ray-curable resin composition, which has excellent flexibility by containing a polyglycidyl ester of an aliphatic long-chain polybasic acid having 8 to 50 carbon atoms as an essential component. The present invention relates to a cationic polymerizable energy ray-curable resin composition that provides a resilient and tough coating film having flexibility, impact resistance, and adhesion. Energy ray-curable compositions such as ultraviolet rays or electron beams have attracted attention from the viewpoint of energy saving, resource saving, space saving, pollution control, etc., and active research and development in the fields of inks, paints, and varnishes has been carried out. Along with this, demands for performance have also increased, and in the paint field there is a demand for energy ray-curable resin compositions that have coating performance equivalent to or better than conventional solvent-based paints, but these are not necessarily satisfactory. is not obtained. The present inventors have conducted various studies regarding energy beam curable resin compositions in order to produce a cationic polymerization type energy beam curable resin composition that provides an elastic and tough coating film. It has been discovered that a composition containing a polyglycidyl ester of a polybasic acid provides an excellent cured coating film,
The invention has been completed. The purpose of the present invention is to create a cationically polymerized energy ray-curable resin composition that provides a highly elastic and tough coating film with excellent coating properties, particularly excellent flexibility, softness, impact resistance, and adhesion. It's about providing things. Specifically, it is an object of the present invention to provide a cationic polymerizable energy ray-curable resin composition particularly suitable for printing ink vehicles, paints, varnishes, coatings, and the like. The cationic polymerization energy ray curable composition of the present invention is a conventional cationic polymerization energy ray curable composition containing a compound (sensitizer) that releases an active catalyst that initiates polymerization of a cationic polymerization resin composition upon energy ray irradiation. The curable resin contains 2 to 40% by weight of polyglycidyl ester of aliphatic long-chain polybasic acid having 8 to 50 carbon atoms as an essential component. First, the cationic polymerization type energy ray curable resin composition, which is the main component of the important component of the present invention, is a conventionally known energy ray sensitized resin composition that is polymerized or crosslinked to form a coating film by irradiation with energy rays. A cationic polymerizable composition containing a curing agent (curing catalyst), such as an epoxy resin composition that is polymerized by cationic ring-opening polymerization of an epoxy ring (for example, those described in Japanese Patent Publication No. 17040/1983, and others as a catalyst). There are several known photosensitive onium salts such as those described in Japanese Patent Publication No. 52-14278 and Japanese Patent Publication No. 52-14277. Epoxy resins used in such epoxy resin compositions include conventionally known aromatic epoxy resins, alicyclic epoxy resins, and aliphatic epoxy resins. Particularly preferred aromatic epoxy resins are polyglycidyl ethers of polyhydric phenols or alkylene oxide adducts thereof having at least one aromatic nucleus, and
Examples include glycidyl ether and epoxy novolak resin produced by the reaction of bisphenol A or its alkylene oxide adduct with epichlorohydrin. Particularly preferable alicyclic epoxy resins include at least one
Cyclohexene oxide or cyclopentene oxide-containing compound obtained by epoxidizing a polyglycidyl ether of a polyhydric alcohol having 2 alicyclic rings or a cyclohexene or cyclopentene ring-containing compound with an appropriate oxidizing agent such as hydrogen peroxide or peracid. There is. Typical examples of polyglycidyl ethers include glycidyl ethers produced by reacting hydrogenated bisphenol A or its alkylene oxide adduct with epichlorohydrin. Further, representative examples of cyclohexene oxide or cyclopentene oxide-containing compounds include those represented by the following formula. Particularly preferable aliphatic epoxy resins include polyglycidyl ethers of aliphatic polyhydric alcohols or their alkylene oxide adducts; typical examples include diglycidyl ether of 1,4-butanediol and 1,6-hexane. 1 for aliphatic polyhydric alcohols such as diglycidyl ether of diol, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, ethylene glycol, propylene glycol, and glycerin. Examples include polyglycidyl ethers of polyether polyols obtained by adding a species or two or more alkylene oxides (ethylene oxide, propylene oxide). Furthermore, monoglycidyl ethers of aliphatic higher alcohols, phenol, cresol, butylphenol, or monoglycidyl ethers of polyether alcohols obtained by adding alkylene oxide to these may also be blended as diluents. The epoxy resin composition of the present invention can also be used in combination with each of these aromatic epoxy resins, alicyclic epoxy resins, or aliphatic epoxy resins and polyglycidyl esters of aliphatic long-chain polybasic acids, as desired. Although these can be appropriately blended depending on the performance of the resin, those mainly composed of alicyclic epoxy resin are particularly preferred. The polyglycidyl ester of aliphatic long-chain polybasic acid having 8 to 50 carbon atoms, which is an essential component of the cationically polymerized energy ray-curable resin composition of the present invention, is an aliphatic polybasic acid or dimer acid, epihalohydrin, For example, it is an ester obtained by reaction with epichlorohydrin or methylepichlorohydrin, and a representative example thereof is a polyglycidyl ester of an aliphatic polybasic acid represented by the following formula. HOOC・(CH ₂ ) ₆・COOH, HOOC・(CH ₂ ) ₁₀・
COOH HOOC・(CH ₂ ) ₁₄・COOH、HOOC・(CH ₂ ) ₁₈・
COOH HOOC・(CH ₂ ) ₆・CH=CH・(CH ₂ ) ₆・COOH HOOC・(CH ₂ ) ₆・CH=CH・(CH ₂ ) ₂・CH=
CH・( _CH2 ) ₆・COOH Polyglycidyl esters of dimer acids and highly polymerized acids include linear or branched unsaturated higher fatty acids, such as 3-octenoic acid, Linderic acid, 10-
Undecenoic acid, laurolanic acid, myristoleic acid, thujic acid, palmitoleic acid, arachidonic acid, petroselic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, cetoleic acid,
Nervonic acid, linoleic acid, linoleic acid, eleostearic acid, hiragic acid, moroctic acid, thymnodonic acid, eicotetraconic acid, nisic acid, hiraganic acid, soybean oil fatty acid, linseed oil fatty acid, cottonseed oil fatty acid, tall oil fatty acid, safflower Examples include polyglycidyl esters of dimer acids and highly polymerized acids obtained by polymerizing oil fatty acids, fish oil fatty acids, and the like. These polyglycidyl esters of aliphatic long-chain polybasic acids having 8 to 50 carbon atoms have good compatibility with the cationic polymerizable composition that is the main component, and the polyglycidyl esters of the aliphatic polybasic acids to be blended have good compatibility with the cationic polymerizable composition that is the main component. The blending amount can be varied widely depending on the type of ester and required performance. Generally, the polyglycidyl ester of aliphatic long chain polybasic acid as an essential component of the energy ray curable resin composition of the present invention is 2 to 40%
It is appropriate to contain within the range of 2% by weight.
If the amount is less than 40% by weight, no effect will be obtained, and if it is more than 40% by weight, the inherent performance of the energy ray-cured coating film tends to deteriorate, so the particularly preferred amount is 5 to 30% by weight. If necessary, olefin resins and acrylic resins other than the above-mentioned cationically polymerizable substances may be added to the cationic polymerizable resin composition of the epoxy resin that is a component of the present invention, as long as they do not impair the effects of the present invention. Resins, ester resins, petroleum resins, alkyd resins, polyether resins, polyvinyl chloride resins, polyvinyl acetate resins, and various paint additives can be blended. On the other hand, the energy rays contained in the cationic polymerizable energy ray curable resin composition used in the present invention decompose under energy ray irradiation and release a catalyst that has the effect of causing polymerization or crosslinking of the cationic polymerizable resin. The sensitizer is not particularly limited, but particularly preferred is a group of double salts, which are onium salts that release Lewis acids capable of initiating polymerization upon irradiation. Such compounds basically have the general formula [R ¹ _a R ² _b R ³ _c R ⁴ _d Z] ^+m [MX _o+n ] ^{-m [} wherein the cation is onium and Z is N≡
N, S, Se, Te, P, As, Sb, Bi, O, halogen (e.g. I, Br, Cl), R ¹ , R ² , R ³ ,
R ⁴ is an organic group which may be the same or different; a, b, c, and d are each an integer of 0 to 3; a+b+c+d is equal to the valence of Z; M is a metal or metalloid that is the central atom of the halide complex, and B, P, As, Sb, Fe,
Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr,
Mn, Co, etc. X is a halogen, m is the net charge of the halide complex ion, and n is the number of halogen atoms in the halide complex ion. ]. Such catalyst precursors are known per se,
For example, a compound where Z is N≡N is disclosed in U.S. Patent No.
It is described in No. 3708296, No. 3949143, No. 3794576, etc. Other onium catalyst precursors are described in Belgian Patent No. 828841, Belgian Patent No. 828669, French Patent No. 2270269, etc. The above diazonium compounds are described in the above US patents.
It can be obtained by the method described in No. 3708296, No. 3949143, etc. Compounds where Z is S, Se, Te are described in J. Knapozyk et al., JACS, 91 , 145,
(1969), AL Maycock et al. J. Organic
Chemistry, 35, No. 8, 2532 (1970), Goethals
Bul.Soc.Chim.Belg., 73 , 546 (1964), HM
It can be produced by the method described in Leicstar et al., JACS, 51 , 3587 (1929). Z is P, N, As, Sb,
A typical onium salt that is Bi is J. Goerdeler's
Methoden der Organishen Chimie, 11/12 ,
591-640 (1958), K. Sasse's 12/1, 79-112
(1963). A typical onium salt where Z is halogen is OAPtitsyna
Dokl.Adad.Nauk., SSSR, 163 , 383
(1965), M. Drexler et al. JACS, 75 , 2705
(1953) and others. Examples of other compounds that can be used to initiate the polymerization of epoxides are iodoform, α, α′-
Dibromoparaxylene, bromoform, carbon tetrabromide, hexachloroparaxylene, and U.S. Pat.
3,895,954, bis(perfluoroalkylsulfonyl)methane salts, and organic halogen compounds such as diazonium salts of sulfonylmethane as described in US Pat. No. 3,586,616 and German Patent No. 2,419,274. These sensitizers may be blended in an appropriate amount depending on the required curing speed and the applied curing method.
It is used within a range of about 10% by weight. The energy ray-curable resin composition of the present invention can be coated on the surface of a substrate by a conventional method such as a roll coater, a gravure coater, a gravure offset, a spray, or the like.
It can be applied by methods such as squeezing and dipping. The thickness of the cured coating film is determined depending on the required performance for various substrates, but is suitably in the range of about 0.1 to 20 microns, preferably about 3 to 10 microns. Energy rays used to apply the curable resin composition of the present invention to various substrates to form a cured coating film include ultraviolet rays, electron beams, and radiation. Among these, methods using ultraviolet irradiation are practical. This is the most preferable method. Further, coating film formation using the curable composition of the present invention can be carried out after or while heat treating the substrate, or by applying the curable composition to the substrate, followed by heat treatment and energy ray irradiation. It can also be effectively promoted by combining the following. Furthermore, when coating the composition, it is also possible to use an organic solvent to adjust the viscosity within a range that does not cause any adverse effects such as deterioration of the performance of the energy ray-curable resin composition. The energy ray-curable composition of the present invention contains a polyglycidyl ester of an aliphatic long-chain polybasic acid having 8 to 50 carbon atoms as an essential component, thereby improving the paintability during painting and improving flexibility. A durable coating film with high elasticity and flexibility and impact resistance can be obtained. That is, the energy ray-curable resin composition of the present invention can be used for various applications in which post-processing such as bending, molding, embossing, etc. is often performed after coating and curing the surface of various substrates, or for long-term high-temperature or low-temperature use. It exhibits excellent effects in applications that require durability under conditions. The curable composition of the present invention can be applied to, for example, agricultural films/sheets, plastic sheets/boards, vinyl chloride films for decorative materials, plastic adhesive films, wrapping paper, glass, metal cans, plastics such as steel plates, paper, metals, and glass. It can be used as a protective varnish, finishing varnish, and coating paint for various substrates. Hereinafter, as an example, a cationic energy ray curable resin that does not contain a polyglycidyl ester of an aliphatic long chain polybasic acid will be described. Representative examples of the present invention in which glycidyl esters are blended will be described in more detail, but the present invention is not limited to the following examples. In the examples, "parts" mean parts by weight. Example 1 Cationic polymerization energy ray curable resin (manufactured by Asahi Denka Kogyo, trade name: ADEKA ULTRASET ADX-
8100L (alicyclic epoxy resin + aliphatic epoxy resin)) 70 parts, diglycidyl ester of aliphatic long chain dibasic acid having 16 to 20 carbon atoms (manufactured by Okamura Oil Co., Ltd., product name)
A resin composition consisting of 30 parts of OS Resin-102) and 3 parts of a cationic curing catalyst (manufactured by Asahi Denka Kogyo Co., Ltd., trade name PP-33) was spread on a 2 mm thick hard vinyl chloride resin plate to a film thickness of 5 μm. Applied evenly. Next, use a high-pressure mercury lamp (80W/cm, 4KW) to 10cm below the lamp.
The coating was passed through a distance of 15 m/min at a speed of 15 m/min and irradiated with ultraviolet rays to obtain a coated hard vinyl chloride resin plate with excellent coating film smoothness, post-processability such as vacuum forming, impact resistance, and adhesion. This coated vinyl chloride resin board can be heated to 125℃
Even after vacuum forming into a cylindrical container with a depth of 10 mm, no peeling of the coating film or occurrence of cracks was observed. On the other hand, in a composition containing no diglycidyl ester of an aliphatic long-chain dibasic acid, cracks were observed in the coating film in a post-processing test using vacuum forming. Example 2 80 parts of ultraviolet curable resin (manufactured by Asahi Denka Kogyo, trade name: ADEKA ULTRASET ADK-7200L (alicyclic epoxy resin + aromatic epoxy resin)), diglycidyl, an aliphatic long chain dibasic acid having 28 carbon atoms 20 parts of ester (manufactured by Okamura Oil Co., Ltd., trade name OS Resin-101) and 3 parts of curing catalyst (manufactured by Asahi Denka Kogyo Co., Ltd., trade name PP-33)
The resin composition of the present invention consisting of 100 μm thick was uniformly applied to a 100 μm thick soft vinyl chloride film to a film thickness of 4 μm. Next, a high-pressure mercury lamp (80W/cm,
By irradiating ultraviolet rays by passing through a distance of 10 cm below the lamp at a speed of 20 m/min using a 4KW), a coated soft vinyl chloride film with excellent cured film adhesion, dust resistance, weather resistance, and blocking resistance can be obtained. Ta. This coated soft vinyl chloride film was measured by Sunshine Super Long Run Weather Meter.
Even after 700 hours of weather resistance testing, the cured film showed no minute cracks or peeling, demonstrating excellent durability. Furthermore, as a comparative test, a coated soft vinyl chloride film obtained using the UV-curable composition containing no diglycidyl ester of an aliphatic long-chain dibasic acid was found to have minute cracks in the cured coating in a weather test. Ta. Example 3 90 parts of ultraviolet curable resin (manufactured by Asahi Denka Kogyo Co., Ltd., trade name: ADEKA ULTRASET ADX-7100 (alicyclic epoxy resin + aliphatic epoxy resin)), a dibasic aliphatic long chain dibasic acid having 22 carbon atoms, The resin composition of the present invention consisting of 10 parts of glycidyl ester (manufactured by Okamura Oil Co., Ltd., trade name OS Resin-103) and 3 parts of a curing catalyst (manufactured by Asahi Denka Kogyo Co., Ltd., trade name PP-33) was applied to vinyl chloride for labels and stickers. Film thickness on the printed surface of the manufactured adhesive film
It was applied to a thickness of 5μ. Next, when UV curing is carried out using a high-pressure mercury lamp in the same manner as in Example 2, the urethane solvent-based paint (commercially available), which is said to have good gasoline resistance, weather resistance, gloss, and durability, can be cured. Gasoline resistance, weather resistance, glossiness,
An adhesive film with better durability was obtained. Example 4 Ultraviolet curable resin (manufactured by Asahi Denka Kogyo Co., Ltd., trade name: ADEKA ULTRASET M-215L-1 (alicyclic epoxy resin + aliphatic epoxy resin)) 85 parts, carbon number 16
~20 aliphatic long-chain dibasic acid diglycidyl ester (manufactured by Okamura Oil Co., Ltd., trade name OS Resin-102) 15 parts and a cationic curing catalyst (manufactured by Asahi Denka Kogyo Co., Ltd., trade name PP-33) 3 parts When the composition is applied to a vinyl chloride decorative sheet with wood grain printing to a film thickness of 7 μm and cured with ultraviolet light in the same manner as in Example 2, surface properties such as scratch resistance, solvent resistance, and dust resistance are improved at the same time. A coated vinyl chloride decorative sheet with excellent post-processability such as V-cuts was obtained. Example 5 90 parts of ultraviolet curable resin (manufactured by Asahi Denka Kogyo Co., Ltd., trade name: Adeka Ultraset B-6136J (alicyclic epoxy resin + aliphatic epoxy resin)), diglycidyl ester of linoleic acid dimer (oiled shell epoxy) 10 parts of Epicoat 871 (manufactured by Asahi Denka Kogyo Co., Ltd., trade name), and 10 parts of a cationic curing catalyst (manufactured by Asahi Denka Kogyo Co., Ltd., trade name PP)
-33) A tin printing plate was uniformly top-coated with 3 parts of the resin composition of the present invention to a film thickness of 5 μm, and then cured with ultraviolet light in the same manner as in Example 1. The obtained coated tin plate showed excellent coating performance with no peeling or cracking in drawing processing tests and impact resistance tests. For comparison, the curable composition containing no diglycidyl ester of dimer acid was used, and a cracking phenomenon was observed in the coating film in the drawability test. Example 6 Ultraviolet curable resin (manufactured by Asahi Denka Kogyo Co., Ltd., trade name
ADX-8107 (alicyclic epoxy resin + aromatic epoxy resin)) 93 parts, diglycidyl ester of aliphatic long chain dibasic acid with 20 carbon atoms (manufactured by Okamura Oil Co., Ltd., product name
The curable composition of the present invention, which consists of 7 parts of OS Resin-105) and 3 parts of a cationic polymerization curing catalyst (manufactured by Asahi Denka Kogyo Co., Ltd., trade name PP-33), was applied to a printing board paper in a film thickness.
It was applied uniformly to a thickness of 7μ, and cured with ultraviolet light in the same manner as in Example 1. The resulting glossy printed board showed better processing suitability in a box-making test compared to one that did not contain the aliphatic long-chain dibasic acid diglycidyl ester. Example 7 In Example 1, as a cationic curing catalyst
Similar coating film properties were obtained using the curable composition of the present invention containing 3 parts of diphenyliodonium tetrafluoroborate in place of PP-33. Example 8 Energy ray curable resin containing no polyglycidyl ester of aliphatic long-chain polybasic acid mainly composed of alicyclic epoxy resin (manufactured by Asahi Denka Kogyo Co., Ltd., trade name: ADEKA ULTRASET ADX-7200L or ADX)
-8100L) and diglycidyl ester of aliphatic long chain dibasic acid (manufactured by Okamura Oil Co., Ltd., trade name OS Resin -101)
Cationic polymerization energy ray curable product obtained by adding 3 parts of a curing catalyst (manufactured by Asahi Denka Kogyo Co., Ltd., trade name PP-33) to 100 parts of a resin composition containing 102) in the proportions shown in Table 1. The resin composition was applied to a stretched polypropylene film, and then a high-pressure mercury lamp (80W/cm, 4KW) was applied at a distance of 10cm below the lamp.
The ultraviolet rays were irradiated by passing at a speed of 20 m/min. The cured film (13μ) of the composition of the present invention obtained by peeling off the cured film on this stretched polypropylene film was measured for elongation. In addition, the flexibility and impact resistance of a coated plate cured to a thickness of 5μ on a mild steel plate for coating film testing under similar curing conditions were measured. As is clear from the results shown in Table 1, diglycidyl ester OS resin of aliphatic long chain dibasic acid
The cured film of the composition of the present invention containing 101 and 102 has better elongation, flexibility, and
Impact resistance is greatly improved.

【table】

[Table] Comparative Example 1 6.7 parts of acrylic acid (equivalent to 0.9 mol per epoxy group) in 30 parts of diglycidyl ester of aliphatic long-chain dibasic acid having 16 to 20 carbon atoms (manufactured by Okamura Oil Co., Ltd., trade name: OS Resin-102) , 30 parts of a compound obtained by adding 0.1 part of hydroquinone and 0.2 parts of triethylamine and reacting at 80°C for 15 hours, and an energy beam curable resin (manufactured by Asahi Denka Kogyo Co., Ltd., trade name: ADEKA ULTRASET)
The physical properties of the coating film were investigated in the same manner as in Example 8 using a composition in which 70 parts of ADX-7200L) and 3 parts of a curing catalyst (manufactured by Asahi Denka Kogyo Co., Ltd., trade name PP-33) were added. , flexibility = ×, and impact resistance = ×.

Claims (1)

[Claims] 1. Polyglycidyl ester of aliphatic long-chain polybasic acid having 8 to 50 carbon atoms, cationic polymerizable energy ray-curable epoxy resin composition, releases active catalyst that initiates polymerization of the cationic polymerizable resin composition upon energy ray irradiation A cationically polymerizable energy ray-curable resin composition comprising 20 to 40% by weight of a polyglycidyl ester of an aliphatic long-chain polybasic acid having 8 to 50 carbon atoms. thing.