JPS6241216A - Novel unsaturated phosphoric ester resin - Google Patents

Abstract

PURPOSE:The titled resin excellent in heat resistance, corrosion resistance, dispersibility and adhesiveness and useful for use in paints, adhesives, casting materials, etc., obtained by reacting a compound having an ethylenical double bond and a phosphoric acid group with an epoxy resin. CONSTITUTION:1mol or above or a compound having an ethylenic double bound and a phosphoric acid group in the molecule, represented by the formula [wherein R1 is H or methyl, R2 is COOY, OCOY, OY, Y, CONHY, CO (OCH2CH2)n or CO(OCH2CH2)m-O-Ph (Y is a 1-30C linear, cyclic or branched aliphatic, alicyclic or aromatic hydrocarbon residue which may be substituted with OH, OR or a halogen, R is a 1-8C hydrocarbon residue, and m and n are each 1-5), R3 is H, or a 1-30C linear, cyclic or branched aliphatic, alicyclic or aromatic hydrocarbon residue] is reacted with 1mol of an epoxy resin of a MW of 240-10,000 at 10-150 deg.C in an inert solvent in the presence of a ring opening catalyst (e.g., triphenylphosphine).

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a novel unsaturated phosphate ester resin suitable for use in paints, adhesives, casting materials, fiber reinforced plastics, etc. relates to a novel unsaturated phosphate ester resin which has excellent dispersibility when used as a coating material and excellent adhesiveness when used as a binder/adhesive.

[Conventional technology and problems]

Currently, unsaturated polyester resins are used for many purposes, mainly in the field of fiber reinforced plastics (hereinafter abbreviated as FRP). Among unsaturated polyester resins, vinyl ester resins have excellent heat resistance and corrosion resistance, as well as excellent moldability and processability. It has been used in places where durability and durability are required. In fields such as electrical and electronic engineering, unsaturated polyester resins are often used as paints. Performance such as dispersibility and adhesion to metals, plastics, etc. also becomes an issue.

However, although conventional unsaturated polyester resins have excellent heat resistance and corrosion resistance, they cannot necessarily be said to have satisfactory performance in terms of dispersibility and adhesive properties as described above.

[Means for solving problems]

As a result of intensive studies to solve the above problems, the present inventors found that a compound obtained by reacting an epoxy resin with a compound having both an ethylenic double bond and a phosphoric acid group in one molecule. The inventors have discovered that saturated phosphoric acid ester resins are excellent not only in heat resistance and corrosion resistance, but also in dispersibility and adhesiveness when used as paints, leading to the present invention.

That is, the present invention provides a novel unsaturated phosphate ester resin obtained by reacting a compound having both an ethylenic double bond and a phosphoric acid group in one molecule and an epoxy resin, and further includes: More preferably, the following general formula (R1 is hydrogen or methyl group, R2 is C00Y, 0CO
Y.

OY,,Y-C0N)IY-C0(OCHzCIh
)1%, CO(OCHzCHt)--0-Ph-(Y is OH, OR, carbon number 1 which may be substituted with halogen
~30 linear, cyclic, branched, aliphatic, alicyclic, aromatic hydrocarbon residues, where R is a hydrocarbon residue having 1 to 8 carbon atoms,
ll, n is a number from 1 to 5), R2 is hydrogen or carbon number 1 to 3
A novel unsaturated phosphate ester resin obtained by reacting a compound having a structure represented by 0 linear, cyclic, branched, aliphatic, alicyclic, or aromatic hydrocarbon residues with an epoxy resin. It provides:

Examples of compounds having an ethylenic double bond and a phosphoric acid group in one molecule used in the present invention include vinylphosphonic acid,
vinyl phosphate or the general formula (R is hydrogen or methyl group, R2 is cooy, oco
y.

OY, Y, C0NHY, CO(OCHzGH
z)-1CO(OCHzC)Ig)--0-Ph-(Y
is a linear, cyclic, or branched aliphatic, alicyclic, or aromatic hydrocarbon residue having 1 to 30 carbon atoms that may be substituted with OR, OR, or halogen; however, R is a carbonized residue having 1 to 8 carbon atoms; hydrogen residue, m and n are numbers from 1 to 5), R5 is hydrogen or carbon number 1 to 3
0 linear, cyclic, branched aliphatic, alicyclic, aromatic hydrocarbon residues] and the like. Specific examples of compounds represented by the above general formula include 2
-methacryloyloxyethyl acid phosphate, 2
-Acryloyloxyethyl acid phosphate, 1-
Chloromethyl-2-methacryloyloxyethyl acid phosphate, 1-methyl-2-methacryloyloxyethyl acid phosphate, alkyl-2-hydroxy-3-methacryloyloxypropyl acid phosphate, sesqui(2-methacryloyloxyethyl ) acid phosphate, di(2-methacryloyloxyethyl) acid phosphate, and the like. Of course, it is not limited to these, and those represented by the general formula (1) are preferably used.

The epoxy resin used in the present invention is preferably a compound having two or more epoxy groups in one molecule, and specific examples include bisphenol-type epoxy resin, novolanc-type epoxy resin, cresol-type epoxy resin, and halogenated bisphenol-type epoxy resin. Examples include epoxy resins, aliphatic epoxy resins, spiroacecooled epoxy resins, and urethanized epoxy resins. The epoxy resin is not limited to those mentioned above, and any compound having an epoxy group may be used. Furthermore, a compound having one epoxy group in one molecule may be used as long as the physical properties of the phosphoric acid ester resin of the present invention do not deteriorate.The molecular weight of the epoxy resin that can be used in the present invention is as follows: It is preferably in the range of 340 to 10,000, and particularly preferably in the range of 340 to 4,000.

The unsaturated phosphate ester resin of the present invention is produced, for example, according to the following reaction.

CTo CI C1h OR' OC1hCH
Cut to θ' to O'(R' represents the central skeleton of the epoxy resin) The above formula shows an example where the molar ratio of the hydroxyl group to the epoxy group in the acidic phosphoric acid ester is 2, but it is not limited to this. Rather, the desired product can be obtained if the amount of the compound having both an ethylenic double bond and a phosphoric acid group in one molecule is 1 mol or more per 1 mol of the epoxy resin.

The above method for producing the unsaturated phosphate ester resin of the present invention is an exothermic reaction accompanied by ring-opening addition of an epoxy group, and as the reaction progresses, the molecular weight increases and the viscosity increases. Therefore, by using a suitable solvent, the unsaturated phosphate ester resin of the present invention can be preferably produced. Solvents that can be used at this time include:
There are no particular limitations as long as they are non-reactive, and ketone, ester, ether, etc. can be preferably used. After completion of the reaction, the used solvent may be removed by topping or may be used as is depending on the use case.Also, 2,4,6-tris(dimethylaminomethyl) Tertiary amines such as phenol, ring-opening catalysts such as triphenylphosphine, trialkylphosphine, etc. may also be used. Although the reaction temperature for the above reaction is not particularly limited, it is desirable to carry out the reaction below the boiling point of the solvent used.

In addition, if the temperature is too high, side reactions such as dehydration reactions may occur, which is not desirable. Usually 10 to 150°C, preferably 20 to 12°C.
It is desirable to carry out the process at about 0°C.

The unsaturated phosphoric acid ester resin of the present invention can be used as a paint, an adhesive, a casting resin, a photo-curing/electron beam-curing resin, and a civil engineering resin together with an ethylenically unsaturated compound, if necessary.

Ethylenically unsaturated compounds that can be used with the unsaturated phosphate ester resin of the present invention include styrene, α-methylstyrene, (meth)acrylic acid, (meth)
(Meth)acrylic acid esters such as methyl acrylate, ethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and 2-hydroxyethyl (meth)acrylate, divinylbenzene, trimethylolpropane tri(meth) Acrylate, diethylene glycol di(
Examples include polyols such as meth)acrylate, poly(meth)acrylate, triallylisocyanurate, and the like. Furthermore, reactive oligomers such as epoxy acrylate, polyester acrylate, and urethane acrylate can also be used.

The unsaturated phosphate ester resin of the present invention can be polymerized by a conventional method. That is, thermal polymerization with peroxides such as benzyl peroxide and cumene oxide, azo compounds such as α,α°-azobisisobutyronitrile, α,α°-azobisvaleronitrile, benzoin, benzoin methyl ether, and benzophenone. Examples include photopolymerization using photoinitiators such as, radiation polymerization using electron beams, β-rays, and the like.

〔Example〕

EXAMPLES The present invention will be specifically explained below with reference to Examples and Comparative Examples, but the present invention is not limited only to these Examples.

Example 1 In a 11 separable flask equipped with a stirrer and a cooler, 206 g of mono(2-methacryloyloxyethyl) acid phosphate (acid value 431 mg KOH/g), 93 g of methyl ethyl ketone, and 0 polymerization inhibitor methyl hydroquinone were added.
．． Prepare 52g. A solution of 312 g of bisphenol A type epoxy resin (epoxy equivalent: 188 g/eq) dissolved in methyl ethyl ketone was added dropwise to this solution so as to maintain the liquid temperature at 50°C. After the dropwise addition was completed, the reaction was completed by maintaining the same temperature for 1 hour. Methyl ethyl ketone was distilled off from this product under reduced pressure to obtain unsaturated phosphoric acid ester resin A.

Example 2 Sesqui(2-methacryloyloxyethyl) acid phosphate (acid value 269s+) was used instead of mono(2-methacryloyloxyethyl) acid phosphate in Example 1.
An unsaturated phosphate ester resin B was obtained in the same manner as in Example 1 except that 200 g (gKOH/g) was used.

Example 3 Using the same reactor as in Example 1, 313 g of sesqui(2-methacryloyloxyethyl) acid phosphate
, 141 g of methyl ethyl ketone.

Charge 0.52g of methylhydroquinone. Add to this a novolac type epoxy resin (epoxy equivalent: 180g/eq)
A solution of 240 g dissolved in 100 g of methyl ethyl ketone was added dropwise so that the liquid temperature was maintained at 50°C. Thereafter, unsaturated phosphoric acid ester resin C was obtained in the same manner as in Example 1.

Comparative Example 1 Bisphenol A type vinyl ester (DoeeChem
DERAKAIN 411-45) manufactured by DERAKANE 411-45) was used as a comparative resin.

Comparative Example 2 Novolak type vinyl ester (Dow Chew %
J Delakane 470-36) was used as a comparative example resin.

Reference Example In order to examine the adhesion of the resins of Examples 1 to 3 and Comparative Examples 1 to 2 to metal, 70 parts of each resin, 27 parts of trimethylolpropane triacrylate, and 3 parts of benzoin methyl ether were mixed. Film thickness 25μm with roll coater
After coating on the tin plate, 2 days under high pressure mercury, 10c
The resin was cured by irradiating ultraviolet light at II+. The adhesion to the tin plate was evaluated by the cross-cut test 0.

The results obtained are shown in Table 1.

0th test JIS-ni-5400 (1979)
Table 1 according to [Effects of the invention] The novel unsaturated phosphate ester resin of the present invention has a polar group (phosphoric acid group, phosphoric ester group) introduced into the resin skeleton, and as a result, Dispersibility for pigments, inorganic powders, etc. and adhesion to metals are significantly improved.

In particular, as specifically shown in the examples, it exhibits good adhesion to metals.

Claims (1)

[Scope of Claims] 1. A novel unsaturated phosphoric acid ester resin obtained by reacting an epoxy resin with a compound having both an ethylenic double bond and a phosphoric acid group in one molecule.2. A compound that has both a double bond and a phosphate group has the following general formula ▲ Numerical formula, chemical formula, table, etc. ▼ [R_1 is hydrogen or methyl group, R_2 is COOY, OC
OY, OY, Y, CONHY, CO(OCH_2CH_
2)_n, CO(OCH_2CH_2)_m-O-Ph
-(Y is a linear, cyclic, branched, aliphatic, alicyclic, or aromatic hydrocarbon residue having 1 to 30 carbon atoms that may be substituted with OH, OR, or halogen; however, R is a carbon number 1 -8 hydrocarbon residues, m and n are numbers from 1 to 5), R_3 is hydrogen or a linear, cyclic, branched aliphatic, alicyclic, aromatic hydrocarbon residue having 1 to 30 carbon atoms] The novel unsaturated phosphate ester resin according to claim 1, which is a compound having the structure represented by