JPS62299935A - contact lens - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a contact lens that has excellent oxygen permeability and is difficult to accumulate layers of dirt.

[Conventional technology]

Contact lenses commonly used today are broadly classified into hard contact lenses and soft contact lenses. Various types of hard contact lenses have been widely known, but the one that has been popular for a long time is polymethyl methacrylate (PMMA).
The main product is hard contact lenses. - For the purpose of improving the hydrophilicity of PMMA, soft contact lenses are made using, for example, 2-hydroxyethyl methacrylate (HEMA) or N-vinyl-2-pyrrolidone (14vp
) hydrophilic monomers such as methyl methacrylate) (MM
It is copolymerized with A) etc.

In addition, in recent years, research has been actively conducted to improve the #R transparency of hard contact lenses.
3502, Special Publication No. 56-59450, Special Publication No. 56-40
524 etc., copolymerization of an alkyl acrylate or methacrylate (hereinafter, acrylate or methacrylate will be referred to as (meth)acrylate) such as MA and (meth)acrylate having a siloxane bond in the side chain is the main component. A contact lens is disclosed.

Furthermore, Japanese Patent Publication No. 56-4080tS discloses a contact lens made of alkyl-substituted styrene, a crosslinker, and a plasticizer, and Japanese Patent Publication No. 57-182718 discloses a contact lens made of a styrene monomer and bisphenol-A-dimethacrylate. Contact lenses made of copolymers have been disclosed, and Japanese Patent Laid-Open No. 59-214822 discloses contact lenses made of fluorine-containing styrene polymers or copolymers.

[Problem that the invention seeks to solve]

Each of the above contact lenses has both advantages and disadvantages. In other words, hard contact lenses mainly composed of H6P MMA have many advantages, such as excellent vision correction effects, good durability, easy handling, and good machinability. On the other hand, PMMA
Because it has poor hydrophilicity, wearing it for a long time tends to cause physiological damage to the cornea.

10,000 Although the original purpose of the soft contact lenses, which was to impart hydrophilic properties, was achieved and the wearing comfort was improved,
Due to water content, it becomes difficult to maintain the shape, the vision correction effect decreases, and the durability is inferior. 1. Polymers mainly composed of HEMA do not have sufficient rIR transmissivity, and in order to compensate for this, they have to further increase the water content. Clinical results have also shown that it is likely to cause serious complications for the conjunctiva and conjunctiva.

In addition, contact lenses made by copolymerizing alkyl (meth)acrylates and (meth)acrylates with siloxane bonds in their side chains cover some of the shortcomings of hard and soft contact lenses, and are oxygen permeable. Although there have been some improvements in terms of performance, vision correction effect, durability, and ease of handling, there is some protein sticking and there is a limit to oxygen permeability, so it cannot be used for long periods of time. It is too opaque to be used for continuous wear. Contact lenses made of alkyl-substituted styrene, crosslinkers, and plasticizers, and contact lenses made of copolymers of styrenic monomers and bisphenol-A-dimethacrylate have low oxygen permeability and contain fluorine. Do contact lenses made of styrene-containing polymers 1 or copolymers also exhibit sufficient oxygen permeability? ln0 The present invention was made in order to solve the above-mentioned problems, and the purpose is to have good oxygen permeability,
The purpose of the present invention is to provide contact lenses that do not easily attract dirt.

Means for Solving Problem C] That is, the present invention is a contact lens characterized by being made of a copolymer of comonomers containing the following A) and B)' as an essential fraction of Ik.

A) One or more selected from the styrenes represented by the general formula (I) (provided that Xl, X*, X2, X4, etc. in the formula
' each independently represents a hydrogen atom, a fluorine atom, a carbon number of 1
~8 alkyl group or fluoroalkyl group) B) One or more compounds selected from the group of compounds represented by the general formula (IF) is 0 or 1.
1 is an integer from 1 to 3, p is an integer from 1 to 5, and m is an integer from 1 to 5.
An integer satisfying 0≦m≦3.0≦n≦5 and m + n = 5, R1 is a hydrogen atom or a methyl group, R1, N R
4 and R1 each independently represent an organic group having 1 to 6 carbon atoms) Fraction A in the present invention includes styrene and one or more fluorine atoms or 1 or more carbon atoms in the benzene ring of styrene.
A group of compounds having ~8 alkyl groups or fluoroalkyl groups (hereinafter abbreviated as styrene or nuclear-substituted styrene)
It's okay. The fraction A polymerized by itself to %, PMM
In addition to exhibiting oxygen permeability approximately 10 times higher than that of A, it also has mechanical strength properties close to that of PMMA. however,
It is not possible to obtain the target oxygen permeability with fraction A alone; outstanding oxygen permeability can only be obtained by combining fraction A with fraction B. Although the substituent on the benzene ring does not need to be present, an alkyl group or a fluoroalkyl group having a relatively small number of carbon atoms is effective in widening the intermolecular distance of the copolymer. However, if the carbon chain of the fluoroalkyl group is too long due to the alkyl group, the strength of the copolymer will decrease.
Shape stability also deteriorates. Therefore, the number of carbon atoms is preferably about 1 to 8.
Butyl group, neopentyl group, 2-ethylhexyl group, cyclohexyl group, trifluoromethyl group, 2.2.2-
Trifluoroethyl group, 2.2.2-trifluoro-1
-trifluoromethylethyl group, 1.1.2.2-tetrahydroperfluorooctyl group, etc. are preferred. Further, a fluorine atom or a fluoroalkyl group is effective in increasing oxygen solubility and oxygen permeability. (lit) of these substituents may be at any of the 2nd to 6th positions on the benzene ring, and the number of substituents may be 1 to 5 or unsubstituted.

On the other hand, fraction B is organosiloxanyl (meth)acrylate, and its polymer exhibits very high oxygen permeability. However, homopolymers have low strength and poor shape stability. Therefore, jJ! used alone! is rare, MM
Copolymerization with fractions such as A has been attempted to improve strength, but the oxygen permeability coefficient (DK value) has dropped significantly and the benefits of organosiloxanyl (meth)acrylate have not been fully utilized. . On the other hand, in the present invention, the share B
By copolymerizing styrene or nuclear-substituted styrene of fraction A, a contact lens that suppressed the decrease in DK value and was suitable for continuous wear was obtained. General formula (I)
Middle Q) R", R", R'oLhiR" a, represents an organic group, but when the number of carbon atoms exceeds 7, polymerizability decreases and the strength of the copolymer also decreases. 1, 1 is one of the factors that determines the length of the part that bonds the siloxanyl residue and the (meth)acrylic group, and is preferably 1-1 to 3 from the viewpoint of the stability of the siloxanyl residue and the strength of the copolymer. In other words, when 1=0, the heptadium or copolymer is easily hydrolyzed;
If it is 6 or more, the strength of the copolymer decreases. Further, k represents a long metal skeleton for imparting some hydrophilicity to the polymer, but is preferably 1 or more in order to maintain the strength of the copolymer, and for the same reason, j is 3 or less. is preferred. The value of p is a factor that determines the size of the siloxanyl group, but if p is too large, the degree of polymerization will not increase and the processability of the polymer will also decrease, so it is preferably 1 to 5.

Specific examples of fraction B include trimethylsilylmethyl(meth)acrylate, pentamethyldisiloxanylmethyl(meth)acrylate, methylbis(trimethylsiloxy)silylmethyl(meth)acrylate, and tris(trimethylsiloxy)silylmethyl(meth)acrylate. Acrylate, tris(pentamethyldisiloxanyloxy)silylmethyl(meth)acrylate, trimethylsilylethyl(meth)acrylate, pentamethyldisiloxanylethyl(meth)acrylate, methylbis(trimethylsiloxy)silylethyl(meth)acrylate,
Tris(trimethylsiloxy)silylethyl(meth)acrylate, Tris(pentamethedisiloxanyloxy)silylethyl(meth)acrylate, Trimethylsilylpropyl(meth)acrylate, Pentamethyldisilokquinylpropyl(meth)acrylate, Methylbis(trimethyl) silyloxy)silylpropyl (meth)acrylate, tris(trimethylsiloxy)silylpropyl(meth)acrylate, tris(pentamethyldisiloxanyloxy)silylpropyl(meth)acrylate,
Methylbis(trimethylsiloxy)silylethylglycerol mono(meth)acrylate, Tris(trimethylsiloxy)silylethylglycerol mono(meth)acrylate, Tris(pentamethyldisiloxanyloxy)silylethylmono(meth)acrylate, Methylbis(trimethylsiloxy) ) silylpropylglycerol mono(meth)acrylate, tris(trimethylsiloxy)silylpropylglycerol mono(meth)acrylate, tris(pentamethyldisiloxanyloxy)silylpropylglycerol mono(meth)acrylate, methylbis(trimethylsiloxy)silylethyl Glycerol ethylene glycol mono(meth)acrylate, Tris() IJ methyl silyl ethyl glycerol ethylene glycol mono(meth)acrylate,
Tris(pentamethyldisiloxanyloxy)silylethylglycerol ethylene glycol mono(meth)acrylate, Methylbis(trimethylsiloxy)silylpropylglycerol ethylene glycol mono(meth)acrylate, Tris(trimethylsiloxy)silylpropylglycerol ethylene glycol mono(meth)acrylate ) acrylate, tris(pentamethyldisiloxanyloxy)silylpropylglycerol ethylene glycol mono(meth)acrylate, pentamethyldisiloxanyl ethylglycerol diethylene glycol 7-(meth)
Acrylate, methylbis(trimethylsiloxy)silylethylglycerol diethylene glycol mono(meth)acrylate, tris(trimethylsiloxy)silylethylglycerol diethylene glycol mono(meth)
Acrylate, Tris(pentamethyldisiloxanyloxy)silylethylglycerol diethylene glycol mono(meth)acrylate, Methylbis(trimethylsiloxy)silylpropylglycerol diethylene glycol mono(meth)acrylate, Tris(trimethylsiloxy)silylpropylglycerol diethylene glycol mono(meth)acrylate Acrylate, tris(pentamethyldisiloxanyloxy)silylpropylglycerol diethylene glycol mono(meth)acrylate, methylbis(trimethylsiloxy)silylethylglycerol triethylene glycol mono(meth)acrylate,
tris(trimethylsiloxy)silylethylglycerol triethylene glycol mono(meth)acrylate,
Tris(pentamethyldisiloxanyloxy)silylnitylglycerol triethylene glycol mono(meth)
Acrylate, methylbis(trimethylsiloxy)silylpropylglycerol triethylene glycol mono(
meth)acrylate, tris(trimethylsiloxy)silylpropylglycerol triethylene glycol mono(meth)ac IJL'-),)lis(hentamethyldisiloxanyloxy)silylpropylglycerol triethylenef IJcol mono(meth)acrylate, Dimethyl(triphenylsiloxy)silylpropyl(meth)
Acrylates, etc. are exposed.

The Union army using share A and share B has a weighted ratio of 10:90 to 90.
: A range of 10 is desirable. That is, when fraction A is less than 10% by weight of both, the mechanical strength of the copolymer is significantly reduced, and when it exceeds 90%, optical oxygen permeability cannot be obtained.

Part A and Part B in the present invention can be copolymerized as a mixture of both, but it is possible to copolymerize only a mixture of the two, but it is possible to improve the mechanical strength, cutting workability, thermal stability of the polymer, and the wearing comfort of the lens. For this purpose, copolymerization with other polymerizable vinyl monomers is also possible. As polymerizable vinyl monomers that can be copolymerized,
For example, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate,
Triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate), 1.4
- Polyfunctional fi such as butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, etc.
g Polyfunctional allyl compounds such as (meth)acrylate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, triallyl cyanurate, triallyl isocyanurate, diethylene glycol bis(allyl carbonate), polyfunctional vinyl such as allyl (meth)acrylate Compounds, methyl (meth)acrylate, ethyl (meth)acrylate, n-globil (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate), 2.2.2-1 Lifluoroethyl (meth)acrylate ) acrylate, 2.2.2-trifluoro-1-trifluoromethylethyl (meth)acrylate, 3,3.4.4.4-pentafluorobutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (Meth)acrylates such as glycerol mono(meth)acrylate, monomethyl itaconate, dimethyl itaconate, (noether itaconate, diethyl itaconate, monophenyl itaconate, diallyl phthalate, methylphenyl itaconate) 1-1 = Vinyl esters such as vinyl acid and vinyl propionate, ethyl vinyl ether, butyl vinyl ether,
Vinyl ethers such as trifluoroethyl vinyl ether and hexafluoropropyl vinyl ether, (meth)acrylic acid, itaconic acid, (meth)acrylic acid amide, N
Examples include -vinyl-2-pyrrolidone, N-vinyl-2.-oxazolidone, and acryloylmorpholine.

Synthetic vinyl monomers other than fractions A-E and fraction B can be used within a range that does not impair the advantages of the present invention, and the amount used is 100 parts by weight of fractions A and B. On the other hand, it is preferable that the amount is 80 parts or less. That is, if it exceeds 80 parts by weight, oxygen permeability will be insufficient and stain resistance will also decrease. If the hydrophilic fraction is excessive, the water content of the polymer will increase and the shape stability performance will also decrease.

In order to copolymerize the above monomer systems, various commonly used radical polymerization initiators are used.
It is also possible to add a photosensitizer and polymerize by UV irradiation.
It is determined by considering the polymerization behavior of the monomer system. In addition, a commonly used method can be used to copolymerize this monomer system and mold it into a contact lens. After copolymerizing a 7-mer containing a polymerization initiator in a suitable 'flu vessel such as a test tube to obtain a round bar or a block, cutting and cutting are performed.
The lens can be processed into a lens that matches the prescription by mechanical processing such as polishing. It is also possible to directly mold contact lenses by mold polymerization by injecting a polymer containing a polymerization initiator into the space created by two molds. When (co)polymerizing something with a large volume, internal strain tends to occur, so it is reasonable to use water as a heating medium in order to control the reaction and obtain a uniform material.

It is also possible to add a layer coloring agent such as a dye or a lubricant such as an ultraviolet absorber to the above-mentioned hexamer system and polymerize it.

1. The surface of the completed lens is chemically treated with silicic acid or alkali, and by low-temperature plasma treatment.
The lens surface can be modified. Furthermore, the wearing comfort can be improved by graft-polymerizing a hydrophilic upper layer onto the surface treated with low-temperature plasma or by graft-polymerizing a hydrophilic upper layer onto the surface in low-temperature plasma.

[For production]

Organosiloxanyl (meth) of fraction B in the present invention
Acrylates are polymerizable polymers with very bulky substituents. Therefore, since the copolymer containing the heptamer has the bulky side @, it has a large porosity and exhibits high oxygen permeability. In addition, since this substituent has a small surface energy and a high oxygen solubility, it is considered that this substituent contributes to further improving the DK value. Styrene or nuclear-substituted styrene of 10,000 fraction A has a polymeric body that has excellent mechanical strength and machinability, and is effective in maintaining the shape and improving machinability of contact lenses.

Furthermore, since the styrene skeleton has superior rigidity compared to straight-chain alkyl groups, when copolymerized with Preparation B, the bulky effect of Preparation B can improve oxygen permeability without compromising mechanical strength. I believe that this is fully demonstrated. In addition, it is believed that the low surface energy of the polymer prevents the deposition of foreign substances such as proteins and inhibits the proliferation of bacteria.

〔Example〕

Hereinafter, the present invention will be explained in detail based on Examples, but the present invention is not limited to these scopes. In addition, parts in the examples represent parts by weight.

Example-1 40 parts of P-methylstyrene, 50 parts of methylbis(trimethylsiloxy)silylpropyl methacrylate, 5 parts of 2-hydroxyethyl methacrylate, and 5 parts of ethylene glycol dimethacrylate were mixed well at room temperature, and azobis(2,4-dimethyl Valeronitrile) (ABvl
o, 5i-i were added and stirred until uniform. This mixed solution was poured into a glass test tube, the inside of which was filled with nitrogen, and then sealed. This test tube was immersed in a hot water bath whose temperature was controlled by a program controller, and was heated to 30°C for 4 hours and 62°C for 5 hours.
Heated for 2 hours at 35℃, 2 hours at 40℃, 2 hours at 50℃, 1.5 hours at 60℃, 2 hours at 80℃, and then heated at 105℃ for 2 hours in an atmospheric furnace. I did it.

A round bar of the obtained copolymer was cut, cut and polished to produce a contact lens.

For lens evaluation and testing, a disk with a diameter of 10 to 12 meters and a thickness of 12 meters was used, and the following items were measured.

Oxygen permeability coefficient (DK value): Xertez Corp
MOD E L 2110 (M
ulti-range analyzer Dt
sgOIV8dOxygsn) was used. As a result, DKfIIL is 7.51 X 1 G-1011/
(8TP) *cm7'a/l・sea a■Hg and friends.

Vickers hardness (nv): Manufactured by Taiyo Tester Co., Ltd.
A Vickers hardness tester was used. As a result, HV is 11.5
Met.

The test piece was immersed in physiological saline containing 12% stain-resistant double albumen lysozyme at 37° C. for 7 days, and the amount of adhesion was measured from the change in absorbance at 280 nm.

As a result, no adhesion of lysozyme was observed.

Example 2 45 parts of styrene, 50 parts of methylbis(trimethylsiloxy)silylglobylglycerol monomethacrylate) and 5 parts of triethylene glycol dimethacrylate were mixed well at room temperature, and azobis(isobutyronitrile) (
5 parts of AIBN]α was added and stirred to make it homogeneous. This mixed solution was poured into a glass test tube, the inside of which was purged with nitrogen, and then sealed. This test tube was immersed in a hot water bath whose temperature was controlled by a program controller, and heated to 55°C for 5 hours.
℃ for 3 hours, 60℃ for 6 hours, 70℃ for 3 hours, 80℃
The mixture was heated for 2 hours at 105° C. in an atmospheric furnace for 2 hours to conduct polymerization. Contact lens creation/evaluation/
The test was conducted in the same manner as in Example-1. As a result, D.K.
The value is 7.27 xl 0-”d(BTP)”cm/Cd
l"aeceIHHg, Hv was 150, and no lysozyme adhesion was observed.

Example-3 55 parts of pentafluorostyrene" parts, l")su()IJ methylcytetraxy)silylpropyl methacrylate,
10@ of triethylene glycol dimethacrylate were mixed well at room temperature, and 5 parts of t-butyl peroxyneodecanoate α was added to make the mixture homogeneous. Polymerization, evaluation, and testing were conducted in the same manner as in Example-1. As a result, the DK value is a 5
4 x 10-10. d (8TP) ・cm/d ++
sec * vm Hg, Hv is 1α9. No adhesion of lysozyme was observed.

Example-4 50 parts of P-isopropylstyrene, 35 parts of pentamethyldicloxanylethyl methacrylate, 1 part of methacrylic acid
0 parts of ethylene glycol dimethacrylate and 5 parts of ethylene glycol dimethacrylate were mixed well at room temperature, and 5 parts of ABVNα was added and stirred to make the mixture uniform. Polymerization, evaluation, and testing were conducted in the same manner as in Example-1. As a result, the DK value is 7.50 x 10-”at
(8TP) acr11/cJ ・seasmI (g,)
Iv was 11.2, and no lysozyme adhesion was observed.

Example-5 50 parts of P-trifluorostyrene, 35 parts of tris(pentamethyldisiloxanyloxy)silylpropyl methacrylate, 10 parts of N-vinyl-2-pyrrolidone, and 5 parts of ethylene glycol dimethacrylate were mixed well at room temperature. , 5 parts of ABVNα were added to make the mixture uniform. Polymerization, evaluation, and testing were conducted in the same manner as in Example-1. the result,
DK value is a51 x 10-IotIlt(8TP)・
m/c1sea ・w+Hg.

HV was 11.6, and no lysozyme adhesion was observed.

Example-6 35 parts of styrene, 65 parts of lis(trimethylsiloxy)silylpropyl methacrylate, 5 parts of 2,2.2-trifluoro-1-trifluoromethylethyl methacrylate
1 part and 5 parts of tetraethylene glycol dimethacrylate were mixed well at room temperature, and 5 parts of ABVNα was added thereto to make the mixture homogeneous. Polymerization, evaluation, and testing were conducted in the same manner as in Example-1. As a result, the DK value is 6.52 x 10−” −
(8TP) Φcm/al ・5ea-+w+Hg,
Hv was 1 (14, no lysozyme adhesion was observed).

Example-7 60 parts of P-methylstyrene, 20 parts of methylbis(trimethylsiloxy)silylpropylglycerol ethylene glycol monomethacrylate, 15 parts of methyl methacrylate, and 5 parts of diethylene glycol dimethacrylate were mixed well at room temperature, and ABVN was added and stirred until homogeneous. And so. Polymerization, evaluation, and testing were conducted in the same manner as in Example-1.

As a result, the DK value was 5.94 x 10-” aI7!
(8TP) -tm/cd ・sea a g Hg
, HV was 1[L9, and no lysozyme adhesion was observed.

Example-8 The lens base material obtained in Example-3 was depressurized to αI Torr vacuum in a plasma polymerization apparatus, and a discharge frequency of 115 was applied while flowing argon gas at 107 (8 TP)/-.
A low-temperature plasma treatment was performed at 6 MHz and a discharge power of 30 W for 30 seconds. Then, while continuing the glow discharge,
107 (8TP) of N-vinyl-2-pyrrolidone at 5°C
)/-, graft polymerization was carried out on the surface of the substrate for 90 seconds.

As a result, the DK value is a 49 X 10""'y/(S
TP) 0cns/cd @ sea amHg,
Hv was 1α6, and no lysozyme attachment was observed.

Example-9 The lens base material obtained in Example-7 was subjected to low-temperature plasma treatment under the same conditions as in Example-8. Next, the glow discharge was stopped, and 2-hydroxyethyl methacrylate was supplied at 12 td (8 TP)/- at 30 to 35[deg.] C., and graft polymerization was carried out on the surface of the substrate for 60 seconds.

As a result, the DK value is 5.88
P) ・am/cnesec esmHg, Hv is 1
18, and no lysozyme adhesion was observed.

Comparative Example-1 35 parts of tris(trimethylsiloxy)silylpropyl methacrylate, 5 parts of methyl methacrylate 55J2-hydroxyethyl methacrylate, and 5 parts of tetraethylene glycol dimethacrylate were mixed well at room temperature,
5 parts of AB V N O were added and stirred until homogeneous.

Polymerization, evaluation, and testing were conducted in the same manner as in Example-1. As a result, the DK value is 1.52 x 10''' m (ST
P) ・Rust/1rA-sec ・■Hg, Hy were 12.1, and no lysozyme adhesion was observed.

Comparative example-2.

96 parts of styrene and 4 parts of ethylene glycol dimethacrylate were mixed well at room temperature, and 5 parts of ABVNa were added and stirred to make the mixture homogeneous. Polymerization, evaluation, and testing are as per Example-
The same procedure as 1 was carried out. As a result, the DK value is 4.5
10-” m (8'l'P) ・cttr/cJl ・
sea"ll11H[, HV was 19.5, and lysozyme attachment 1 was 011 μf/-.

〔Effect of the invention〕

As described above, the single copolymer of a comonomer containing styrene or a nuclear-substituted styrene and an organosiloxanyl (meth)acrylate in the present invention has a steric effect due to the bulkiness of the styrene skeleton and the siloxanyl group,
It exhibits extremely high oxygen permeability due to increased oxygen solubility due to low surface energy. As a result, when molded into a contact lens, a contact lens was obtained that could supply light to the cornea even during sleep, and could be worn continuously for a long period of time. In addition, due to the reduction in surface energy, it becomes difficult for protein and other dirt to accumulate, making contact lens care, which was traditionally considered complicated, easier.
This is a major factor in achieving continuous wear.

Furthermore, by taking advantage of the characteristics of the contact lens material of the present invention, it is expected that it will be applied to oxygen enrichment membranes, sludge separation membranes, and biomaterials.

that's all

Claims (1)

[Scope of Claims] A contact lens comprising a copolymer of comonomers containing the following A) and B) as essential parts. A) One or more types selected from the styrenes represented by the general formula [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [ I ] (However, X^1, X^2, X^3, X^ in the formula 4 and X^5 each independently represent a hydrogen atom, a fluorine atom, an alkyl group having 1 to 8 carbon atoms, or a fluoroalkyl group) B) One or more compounds selected from the group of compounds represented by the general formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [II] (However, in the formula, j is an integer from 0 to 3, k is 0 or 1,
1 is an integer of 1 to 3, p is an integer of 1 to 5, m and n are
An integer satisfying 0≦m≦3, 0≦n≦3 and m+n=3,
R^1 is a hydrogen atom or a methyl group, R^2, R^3, R
^4 and R^5 each independently represent an organic group having 1 to 6 carbon atoms)