JPH0782216A - New (meth)acrylic acid ester, its composition, its production, curable resin composed of the ester and curable resin composition - Google Patents

Abstract

PURPOSE:To provide a new (meth)acrylic acid ester useful as a monomer component for a UV-curable resin or a monomer or comonomer of general resin materials. CONSTITUTION:A new (meth)acrylic acid ester expressed by the formula 1 (R<1> to R<3> are 1-15C alkyl; R<4> is H or methyl), e.g. 2-t-butyl-2,5,5-trimethylhexyl methacrylate. The (meth)acrylic acid ester of the formula I can be produced by hydrogenating a tertiary carboxylic acid of the formula II and esterifying the obtained alcohol of the formula III with methacrylic acid or acrylic acid. The compound of the formula I is suitable for various uses such as a constituent component or raw material component of paint, ink, tacky adhesive, resin coating material, laminating material, organic glass material, laser disk, contact lens, acrylic glass fiber, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel (meth) acrylic acid ester, and more particularly to a tert-alkyl methyl ester of acrylic acid or methacrylic acid (that is, having a structure having a large degree of branching and a complex structure). Then
It is a special alkyl group ester with a large steric hindrance, and has excellent functions or unique properties such as effective suppression of volume shrinkage due to curing when used as a monomer component of light or thermosetting resin. And an industrially useful (meth) acrylic acid ester having

Therefore, the (meth) acrylic acid ester of the present invention is particularly useful as a monomer component (main raw material or additive) for a UV curable resin, or as a monomer or comonomer for a more general resin material. , For example, paints, inks, adhesives, resin coating materials and laminated materials (protective films, adhesive layers, ink layers, charge transfer layers and other functional layers), organic glass materials, laser disks, contact lenses, acrylics It can be suitably used for various purposes as a constituent component or raw material component of glass fiber or the like (additive component such as main raw material monomer, comonomer or resin improving agent).

The present invention also relates to a method for industrially advantageously producing the (meth) acrylic acid ester.

The present invention relates not only to the individual compounds of the (meth) acrylic acid ester, but also to a mixture of them at an arbitrary ratio, or containing the (meth) acrylic acid ester as a main component or an additive component. The present invention also relates to a mixture or a composition, and particularly to a curable resin composed of the (meth) acrylic acid ester or a curable resin composition containing the curable resin, as an example of a suitable application.

[0005]

2. Description of the Related Art As (meth) acrylic acid ester,
Traditionally, acrylic acid and methacrylic acid methyl ester, ethyl ester, butyl ester, isobutyl ester,
A large number of linear or slightly branched alkyl group esters such as tert-butyl ester, 2-ethylhexyl ester, and isooctyl ester are known. These alkyl (meth) acrylates take advantage of various properties such as ease of polymerization and curing by heat and light, viscous adhesion due to polymerization and curing, and transparency of polymers, cured products, oligomers, etc. It is widely used in various fields as a component for curable resins such as, or as a more general polymerization monomer or comonomer, for example, paints, inks, adhesives, organic glasses, contact lenses, acrylic glasses. It is used for a wide variety of applications such as fibers, laser disks, and other components of various laminated materials (protective film, adhesive layer, ink layer of thermal transfer tape, charge transfer layer of photoconductor, etc.).

However, in the conventional (meth) acrylic acid alkyl ester as described above [that is, one having a linear or relatively small degree of branching as an alkyl group (group corresponding to an alcohol residue) of the ester] However, depending on the application, sufficient performance may not be obtained. For example, when used as a monomer component of a curable resin such as a UV curable resin, the degree of freedom of the alkyl group is large, so curing during light irradiation, etc. In this case, the volumetric shrinkage of the resin material was large, which made it difficult to precisely design the dimensions and shape, and the resin layer was easily peeled off from the substrate.

Therefore, as a (meth) acrylic acid alkyl ester which does not have such a problem or can suppress such a problem, an alkyl group having a structure with a large degree of branching and a large steric hindrance (ie, degree of freedom) Since an ester having an alkyl group having a small value of () as an alcohol residue was considered, the present inventor extensively investigated such (meth) acrylic acid ester. As a result, (meth) acrylic acid alkyl esters having an alkyl group having a sufficiently large steric hindrance and having a structure with a large degree of branching that satisfies such requirements as the alcohol residue of the ester are known in the art. It turned out not to be.

[0008]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and a first object of the present invention is to easily solve the above problems due to a small volume shrinkage during polymerization and curing. A new (meth) acrylic acid, which is an ester of an alkyl group with a large degree of branching and has a large degree of steric hindrance, where various new or useful functions and properties can be expected. To provide the ester.

The present invention is not limited to the individual compounds of the novel (meth) acrylic acid alkyl ester, but also a mixture of the alkyl ester or a composition containing the ester as a main component, and further, a composition of the alkyl ester. As a suitable application example that takes advantage of its excellent characteristics, the volume shrinkage during polymerization and curing is small, the adhesion between the cured resin film and its substrate is excellent, and the precise design of the size or shape of the resin material is easy. It is also an object to provide a curable resin composed of the ester or a curable resin composition containing the ester as a main raw material, an additive, an improving agent, or the like, which has excellent performance.

The present invention also establishes a method for industrially producing the above-mentioned (meth) acrylic acid ester of the present invention (a single compound, a mixture, or a composition containing this as a main component). It is also intended to provide.

[0011]

Means for Solving the Problems The inventors of the present invention have conducted earnest studies to solve the above-mentioned problems (problem of volume shrinkage during polymerization and curing) as found in conventional alkyl (meth) acrylates. As a result, t of acrylic acid or methacrylic acid
Synthesis of various novel (meth) acrylic acid esters called ert-alkyl methyl esters, which are esters of alkyl groups with large steric hindrance (alkyl groups with a small degree of freedom) that have a sufficiently large degree of branching. I succeeded in doing so.

Therefore, when these novel (meth) acrylic acid alkyl esters were applied as a monomer component and an improving agent for UV-curing resin, as expected, actually, light irradiation and volume contraction during curing (polymerization) were effective. I found that it can be suppressed. It was also confirmed that volume shrinkage can be sufficiently suppressed by curing (polymerization) by heat other than light. As a result, it has been found that by suppressing this volume shrinkage, precise design of the size and shape of the resin material can be remarkably facilitated and the adhesion between the substrate and the resin layer can be remarkably improved.

That is, it has been found that the (meth) acrylic acid ester of the present invention is a novel and industrially very useful compound or material which can be suitably used for the above various uses.

Furthermore, the present inventor has found that these novel (meth)
As a result of various studies on a method for producing an acrylic acid alkyl ester, various tertiary compounds such as a tertiary carboxylic acid having 9 or 13 carbon atoms or a mixture thereof described in JP-A No. 64-9955. It was confirmed that the method obtained by reacting an alcohol (tert-alkylmethanol) obtained by hydrogenating a carboxylic acid or a mixture thereof with acrylic acid and / or methacrylic acid to esterify is a very useful method in practice. did.

The present inventor has completed the present invention mainly based on the above findings.

That is, the present invention provides the following general formula [I]:

[0017]

[Chemical 4] (However, R ¹ , R ² and R ³ in the formula [I] have 1 to 1 carbon atoms.
The 15 alkyl groups may be the same or different from each other, and R ⁴ is a hydrogen atom or a methyl group. The present invention provides a novel (meth) acrylic acid ester represented by

The (meth) acrylic acid ester (alkyl ester) of the present invention may be an individual isolated compound (acrylic acid ester, methacrylic acid ester) or a mixture of two or more kinds. Further, it may be a (meth) acrylic acid ester composition containing or containing at least one kind as a main component, and can be obtained or used in various forms.

Further, the present invention is, as a preferred example of the use of the (meth) acrylic acid ester of the present invention, various curable resins comprising the (meth) acrylic acid ester, or the (meth) acrylic acid ester. Provided are various curable resin compositions containing as a monomer component, a comonomer component, an additive or an improving agent.

Furthermore, the present invention provides the following general formula [II] as an example of a suitable method for producing the (meth) acrylic acid ester of the present invention.

[0021]

[Chemical 5] (However, R ¹ , R ² and R ³ in the formula [I] have 1 to 1 carbon atoms.
The 15 alkyl groups may be the same or different from each other. ) The following general formula [III] obtained by hydrogenating a tertiary carboxylic acid

[0022]

[Chemical 6] (However, R ¹ , R ² and R ³ in the formula [III] have the same meanings as described above.) The esterification reaction of the alcohol represented by methacrylic acid and / or acrylic acid. A method is also provided.

R ¹ and R ² shown in the above formulas [I] to [III]
And R ³ are each an alkyl group having 1 to 15 carbon atoms, and the alkyl group may be a linear, branched, cyclic, or cyclic alkyl group having various structures. It may have a structure, specifically, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, various types of pentyl. Group, hexyl group, heptyl group, octyl group, nonyl group, decyl group,
Undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, cyclopentyl group, methylcyclopentyl group, cyclohexyl group, methylcyclohexyl group, ethylcyclohexyl group, cyclooctyl group and other cycloalkyl groups, cyclohexylmethyl group, cyclohexylethyl group, Examples thereof include various alkyl groups having a cyclic structure such as benzyl group, phenethyl group and phenylbutyl group. These R ¹ , R ² and R ³ may be the same groups, or some or all of them may be different. R ⁴ in the above formula [I] is a hydrogen atom or a methyl group.

That is, as the compound of the present invention represented by the formula [I], a wide variety of alkyl acrylates and alkyl methacrylates can be prepared according to the kind and combination of R ¹ , R ² , R ³ and R ^4. However, in any case, the (meth) acrylic acid ester of the present invention is represented by R ¹ R ² R ³ C—CH ₂ — as an alcohol residue of the ester.
The novel compound is characterized by having an ert-alkylmethyl group (that is, an alkyl group having a large branching degree and having a complicated structure and having large steric hindrance).

Among the (meth) acrylic acid esters of the present invention, examples of typical compounds thereof include, for example, neopentyl acrylate, neopentyl methacrylate,
2,2-dimethylbutyl acrylate, 2,2-dimethylbutyl methacrylate, 2,2,3-trimethylbutyl acrylate, 2,2,3-trimethylbutyl methacrylate, 2,2,3,3-tetramethylbutyl acrylate, 2 , 2,3,3-Tetramethylbutyl methacrylate, 2-ethyl-2,3,3-trimethylbutyl acrylate, 2-ethyl-2,3,3-trimethylbutyl methacrylate, 2-isopropyl-2,3-dimethylbutyl Acrylate, 2-isopropyl-2,3-dimethylbutyl methacrylate, 2,2,3,3-tetramethylpentyl acrylate, 2,2,3,3-tetramethylpentyl methacrylate, 2,2,3,4-tetramethyl Pentyl acrylate, 2,2,3,4-tetramethylpentyl Methacrylate, 2,2,4,4-tetramethyl-pentyl acrylate, 2,2,4,4-tetramethyl-pentyl methacrylate, 2-ethyl-2-
Methylpentyl acrylate, 2-ethyl-2-methylpentyl methacrylate, 2-ethyl-2,3,3,3
5, -tetramethylhexyl acrylate, 2-ethyl-2,3,3,5, -tetramethylhexyl methacrylate, 2-neopentyl-2,5-dimethylhexyl acrylate, 2-neopentyl-2,5-dimethylhexyl methacrylate, 2-neopentyl-2,3,3-
Trimethylpentyl acrylate, 2-neopentyl-
2,3,3-trimethylpentyl methacrylate, 2-
Isopropyl-2,3,5,5-tetramethylhexyl acrylate, 2-isopropyl-2,3,5,5-tetramethylhexyl methacrylate, 2-tert-butyl-2,5,5-trimethylhexyl acrylate,
2-tert-butyl-2,5,5-trimethylhexyl methacrylate and the like can be exemplified.

The (meth) acrylic acid ester of the present invention is
It is not necessarily limited to each isolated single compound of the alkyl acrylate and the alkyl methacrylate represented by the formula [I], and a mixture of any two or more of them, or A mixture (or composition) containing any one or more of them as a main component, and further a mixture (or composition) containing any one or more of them. Can be used or manufactured.

For example, as described below, a carboxylic acid mixture containing one or more corresponding tertiary carboxylic acids (R ¹ R ² R ³ C-COOH) is hydrogenated to give a corresponding highly branched alcohol ( R ¹ R ² R ³ C—CH ₂ —OH) is used as an alcohol mixture containing one or more kinds, and acrylic acid and / or methacrylic acid is reacted with this to esterify to form one or more kinds. It is possible to obtain a mixture containing a given (meth) acrylic acid ester of the present invention, but the mixture thus produced also has the (meth) acrylic acid of the present invention.
Considered as an acrylic ester embodiment. That is, each predetermined ester may be isolated from the thus-prepared predetermined (meth) acrylic acid ester-containing material, or may be appropriately used as a mixture as the case may be. Can be used as a product having a purity, a degree of purification, or a composition.

The (meth) acrylic acid ester of the present invention is
The general production method is not particularly limited, and it can be produced from various appropriate raw materials by various synthetic methods or routes.

For example, when the predetermined alcohol represented by the general formula [III] is available, it is esterified by reacting it with acrylic acid or methacrylic acid (or a mixture thereof) according to a conventional method, or The desired (meth) acrylic acid ester of the present invention can be obtained by transesterification by reacting with a lower alkyl ester of (meth) acrylic acid such as methyl acrylate or methyl methacrylate.

At this time, when an alcohol having an appropriate structure is not available or is insufficient, a predetermined alcohol represented by the above formula [III] is appropriately synthesized, and the esterification reaction or ester is carried out as described above. A method utilizing an exchange reaction may be adopted. In this case, there are various methods for synthesizing the predetermined alcohol (R ¹ R ² R ³ C—CH ₂ —OH), but in practice, the tertiary alcohol represented by the formula [II] is usually used. A method of synthesizing by hydrogenation of carboxylic acid is preferably used.

The tertiary carboxylic acid (R ¹ R ² R ³ C-
COOH) can be easily obtained, for example, by Koch reaction using an appropriate branched olefin as a raw material. At that time, as a branched olefin as a raw material, in addition to a commercially available product, for example, a branched olefin obtained by an oligomerization (dimerization, trimerization, etc.) of a lower molecular weight branched olefin can be used to obtain a wide variety of tertiary olefins. It becomes possible to obtain a carboxylic acid.

As an example of the method for industrially advantageously producing the (meth) acrylic acid ester of the present invention, a method for producing from a tertiary carboxylic acid (hereinafter referred to as method A) will be described below.
Will be described in detail.

This method (method A) is the same as the above formula [II].
(Ie R¹R²R³Third represented by C-COOH)
The primary carboxylic acid is hydrogenated to give the above formula [III] (ie,
Chi, R¹R²R³C-CH₂-OH) alcohol represented
(Ie corresponding tert-alkylmethanol)
And then add the alcohol to methacrylic acid and / or alcohol.
By reacting with acrylic acid (esterification reaction),
Various desired (meth) acrylic acid esters of the present invention
Tell [ie R¹R²R³C-CH₂-OCOCH = C
H₂Or R¹R²R³C-CH₂-OCOC (CH₃) =
CH₂] Is the method of obtaining. In addition, these smells
And R¹, R²And R³Is as described above
(The same applies below). However, the above-mentioned third-class mosquito used as a raw material
Rubonic acid is used when hydrogenating to the alcohol.
And the carbon-carbon unsaturated bond is R¹, R², R ³To become
Na (ie R¹, R²And R³Part of
All had carbon-carbon unsaturated bonds before their hydrogenation.
Use unsaturated tertiary carboxylic acid as raw material
You can also do it.

In this method A, the tertiary carboxylic acid used as a raw material may be pure,
A mixture containing one kind or two or more kinds may be used, and one having an appropriate purity or composition may be appropriately used. The alcohol, which is an intermediate product, may be isolated and then used for the ester, but the ester may be appropriately used as a mixture, and various measures may be taken depending on the situation. Of course, a predetermined alcohol (R ¹ R ² R) which is an intermediate product
^{When 3} C-CH ₂ -OH) is available, a method of esterifying it to obtain a desired (meth) acrylic acid ester can also be suitably adopted as an aspect of this method A.

The tertiary carboxylic acid (R ¹ R ² R ³ C--C
The hydrogenation reaction of (OOH) to alcohol is represented by the following general formula [IV].

R ¹ R ² R ³ CCOOH + 2H ₂ → R ¹ R ² R ³ CCH ₂ OH + H ₂ O [IV] The esterification reaction is represented by the following general formula [V].

R ¹ R ² R ³ CCH ₂ OH + HOCOCR ⁴ = CH ₂ → R ¹ R ² R ³ CCH ₂ OCOCR ⁴ = CH ₂ + H ₂ O [V] (wherein R ⁴ is a hydrogen atom or methyl That is, the target tertiary carboxylic acid is a target (meth) acrylic acid ester (R ¹ R ² R ³ CCH ₂ OCO).
Those corresponding to CR ⁴ = CH ₂ (may be a mixture) may be used. The same applies to the intermediate product or alcohol corresponding to the esterification raw material.

Therefore, the specific structure (type) of the tertiary carboxylic acid or alcohol to be used as the raw material depends on the (meth) acrylic acid ester of the present invention including the various esters mentioned above. Since the structure (formula [I]) and the reaction formulas ([IV] and [V]) can be easily clarified, specific examples of these tertiary carboxylic acids and alcohols are omitted.

The tertiary carboxylic acid may be a commercially available product or a synthetic product, and may be used alone or in a mixture of two or more kinds. May be used as a mixture containing one or more kinds (for example, a mixture containing another carboxylic acid, or a mixture containing a tertiary carboxylic acid obtained by Koch reaction). In fact, for example, a carboxylic acid mixture containing a tertiary carboxylic acid having 9 or 13 carbon atoms as a main component, which is produced by the method described in JP-A-64-9955, can be preferably used. .

Similarly, as the alcohol used as the raw material of the ester, either a commercially available product or a synthetic product may be used, and one kind may be used alone, or a mixture may be used.

The hydrogenation reaction is carried out by a method using a hydrogenation reagent such as LiAlH ₄ or Zn, Ni, C or the like.
It can be easily achieved according to a conventional method such as catalytic hydrogenation using various known hydrogenation catalysts of carboxylic acids to alcohols such as o, Sn, Pt, Pd and Rh.

The esterification reaction can also be carried out according to a known method, and can be easily achieved by the ester conditions using a usual acid catalyst. However, since acrylic acid or methacrylic acid used as a raw material and acrylic acid ester or methacrylic acid ester to be produced are easily polymerized, it is desirable to add an appropriate amount of a polymerization inhibitor to the reaction.

Examples of the acid catalyst for esterification include sulfuric acid and p-toluenesulfonic acid, but the acid catalyst is not limited to these.

Examples of the polymerization inhibitor include, but are not limited to, phenothiazine, p-methoxyphenol, hydroquinone and the like.

The above-mentioned esterification reaction is usually carried out in a suitable solvent, and particularly preferably used solvents include, for example, n-hexane, cyclohexane, benzene, toluene, etc. for the progress of the esterification reaction. A solvent which does not cause any trouble and which can remove the produced water by azeotropic distillation can be mentioned.

This esterification reaction is usually carried out in the range of 80 to 12
Although it can be suitably carried out at a temperature of about 0 ° C., the water produced is azeotropically removed by appropriately setting the temperature near or above the boiling point of the solvent used, or raising the temperature as the reaction proceeds. The method of carrying out while doing is suitably adopted. Usually, the reaction pressure may be selected from reduced pressure to around normal pressure, and a method of accelerating the azeotropic removal of the produced water by reducing pressure is often suitably used.

As described above, the desired (meth) acrylic acid ester can be efficiently and easily synthesized.
When the obtained product is colored, it can be easily decolorized by treating it with, for example, activated carbon.

The product containing the predetermined (meth) acrylic acid ester thus obtained can be used as it is, for example, as a mixture or composition in which the solvent remains, or by removing the solvent, appropriately separating and purifying. And the like, and can be obtained and used as an isolated product of (meth) acrylic acid ester or as a mixture.

The (meth) acrylic acid ester of the present invention is
As described above, it can be used for various purposes. At that time, each compound may be used after being isolated, or may be used as a mixture as it is or as a mixture. That is, the (meth) acrylic acid ester of the present invention may be used alone, in the form of a mixture of two or more kinds in an arbitrary ratio, or in the form of one or two kinds, depending on the purpose of use and the situation. When it is used as a composition containing the above as the main component, it is used in various ways such as when it is used as a composition containing or adding one or more kinds.

The (meth) acrylic acid ester of the present invention is
Like the conventionally known (meth) acrylic acid ester, it can be suitably used as a raw material or a raw material component for the production of various polymers or oligomers or a resin composition containing them. Among them, a curable resin or a cured resin is particularly preferable. It can be suitably used as a raw material component (monomer or comonomer component) of the resin composition. This is because the (meth) acrylic acid ester of the present invention is not limited to being effective as a monomer component or a comonomer component for a curable resin or a curable resin composition,
By using this as the main monomer component or comonomer component, it is possible to suppress (reduce) the volume shrinkage of the resin material during polymerization and curing, and by reducing this volume shrinkage, the adhesion between the cured resin film and its substrate Is sufficiently improved, problems such as peeling between the substrate and the resin film are easily solved, and excellent effects such as easy precision design of the size and shape of the cured product are exhibited. is there. In this way, the use of the (meth) acrylic acid ester of the present invention can effectively realize the suppression of volume shrinkage because the (meth) acrylic acid alkyl ester of the present invention is It should be understood that it is because it has an alkyl group having a large degree of branching and a large steric hindrance (that is, a remarkably small degree of freedom) as an alcohol residue of the ester as compared with the case of an ester. You can

That is, the curable resin and the curable resin composition of the present invention each contain at least one or two or more kinds of the (meth) acrylic acid ester of the present invention as a monomer component or a comonomer component. Other than that, the configuration may be the same as the conventional one. For example, in a conventional acrylic curable resin or curable resin composition, a usual (meth) acrylic acid ester or (meth) acrylic acid is used as a monomer component, but all or one of these monomer components is used. The curable resin or curable resin composition of the present invention can also be obtained by substituting a part with the (meth) acrylic acid ester of the present invention. Therefore, the (meth) of the present invention is used as a monomer component.
Acrylic acid ester alone may be used, or a mixture of the acrylic acid ester and other (meth) acrylic acid ester (conventional type) (for example, carbon number 9 described in JP-A-64-9955). Alternatively, a (meth) acrylic acid ester mixture obtained from a carboxylic acid mixture containing 13 tertiary carboxylic acids as a main component) may be used, and various compositions can be used.

As the curable resin and the curable resin composition,
Generally, a type that is polymerized and cured by light such as UV, a type that is polymerized and cured by heat, or
There are various types such as those that use heat and light.
The curable resin and the curable resin composition of the present invention may be of any of these types, but among them, those of the type that are polymerized and cured by utilizing light, especially UV, especially (meth) acrylic Those of the system are preferred.

When such a curable resin or a curable resin composition is constituted, various substances are usually mixed or added depending on the means of polymerization and curing such as light and heat and the application. It is designed to have a different composition. Generally, in addition to the monomer (or prepolymer) component, it is common to add a crosslinking agent (curing agent) for curing and a polymerization initiator such as a photopolymerization initiator or a thermal polymerization initiator. In addition, a curing accelerator, an additive peculiar to each application, etc. are added depending on the case. Also in the case of the curable resin and the curable resin composition of the present invention, by using the (meth) acrylic acid ester of the present invention as a monomer component or as a part of the monomer component (that is, a comonomer or an additive), It can be similarly configured.

That is, as the cross-linking agent (curing agent) used in the curable resin and the curable resin composition of the present invention, various conventionally used ones can be used. Examples thereof include polyacrylates and polymethacrylates of polyols such as methylolpropane and pentaerythritol. Above all, polyacrylates such as trimethylolpropane triacrylate are preferably used. These are compounded in the curable resin or the curable resin composition in an amount of about 1 to 60% by weight.

When a monomer component is used in addition to the (meth) acrylic acid ester of the present invention, a wide variety of monomer components can be used, and generally, the (meth) acrylic acid ester or cross-linking agent is used. Those which can be copolymerized with the agent (for example, vinyl compound etc.) are preferably used. Among them, usual (meth) acrylic acid ester [for example, methyl ester, ethyl ester, propyl ester, isopropyl ester of (meth) acrylic acid] , Butyl ester, sec-butyl ester, isobutyl ester, tert-butyl ester, pentyl ester, isopentyl ester, tert-pentyl ester, hexyl ester, isohexyl ester, octyl ester, isooctyl ester, cyclohexyl ester) and (meta Acrylic acid are preferably used.

That is, a suitable amount of the (meth) acrylic acid ester of the present invention is added to a conventional curable resin or curable resin composition having a monomer base material of (meth) acrylic acid ester or (meth) acrylic acid. The curable resin or curable resin composition of the present invention can also be constituted by this.

When the (meth) acrylic acid ester of the present invention is used as a comonomer component (additive or resin improver) as described above, the (meth) acrylic acid ester is used with respect to the total amount of the monomer component. Usually, it is desirable to add and contain it in a ratio of 1% by weight or more. If this ratio is too small, the effect of adding the (meth) acrylic acid ester of the present invention will not be sufficiently exerted, and the volume shrinkage during polymerization and curing cannot be sufficiently suppressed.

As the above-mentioned polymerization initiator, various conventionally used ones can be applied, among which light (UV) is used.
Examples of the polymerization initiator include Irgacure 18
4 (manufactured by Ciba Geigy, 1-hydroxycyclohexyl phenyl ketone), Irgacure 651 (manufactured by Ciba Geigy, benzyl dimethyl ketal), Daroc
ur 1173 (2-hydroxy-2-methyl-1-phenylpropan-1-one, manufactured by Merck & Co., Inc.) can be exemplified, but the invention is not limited thereto.
Moreover, examples of the thermal polymerization initiator include benzoyl peroxide and azobisisobutyronitrile, but the thermal polymerization initiator is not limited thereto.

In addition, the curable resin and the curable resin composition of the present invention may contain various components other than the above-mentioned various components (for example, a solvent, a coloring agent such as ink, a pigment, a polymerization accelerator, etc.) as necessary. Agents, curing accelerators, charge transfer agents, fillers, polishes,
Antistatic agents, stabilizers, antioxidants, foaming agents, surfactants, other binder components, viscosity modifiers, etc.) can be appropriately added or included.

As described above, various curable resins and curable resin compositions having compositions suitable for various uses can be obtained.

The (meth) acrylic acid ester of the present invention can be suitably used as a component of the above-mentioned curable resin or curable resin composition, but its use is not limited to these. Instead, it can be applied to various applications such as raw materials for other general polymers and oligomers such as thermoplastic resins.

[0062]

EXAMPLES Next, the present invention will be described more specifically by showing Examples of the present invention and Comparative Examples thereof, but the present invention is not limited to these Examples.

Example 1 Synthesis of 2-t-butyl-2,5,5-trimethyl-1-hexanoic acid 270 g of a mixed solution of 64% by weight of sulfuric acid, 29% by weight of phosphoric acid and 7% by weight of water, and 1st oxidation 2.3 g of copper was charged into an electromagnetic stirring type stainless steel autoclave (capacity: 1 liter) and the air in the autoclave was replaced with carbon monoxide gas, then the temperature was 25 ° C. and the carbon monoxide gas pressure was 15
It was kept at kg / cm ² G and stirred for 3 hours at a rotation speed of 1000 rpm to dissolve cuprous oxide (acid strength = −8.
1-7.5).

Subsequently, while maintaining the temperature and the pressure, an olefin mixture (triisobutylene raw material) having a composition shown in Table 1 and having an olefin having 12 carbon atoms as a main component [IP16
20R, manufactured by Idemitsu Petrochemical Co., Ltd., C ₁₁ or less olefin: 9.1% by weight, C ₁₂ olefin: 86.4% by weight,
C ₁₃ or higher olefin: 4.5% by weight, total: 100% by weight)] 50.4 g was pumped into the autoclave over 90 minutes. The composition of the supplied olefin mixture is shown in Table 1.

The carbon monoxide gas consumed along with the progress of the reaction has a gauge pressure of the carbon monoxide gas of 15 kg / cm ²
Replenished by keeping G. After the supply of olefin was stopped, stirring was continued for another hour. After the reaction was completed, carbon monoxide remaining in the autoclave was removed, and the resulting reaction mixture was diluted with 3 times water. Extraction of this diluted solution was repeated three times with 200 ml of n-hexane.

The extracts were combined and n-hexane was removed from the extracts to obtain a crude carboxylic acid composition.

Then, this crude carboxylic acid composition was purified by cooling crystallization to obtain 2-t-butyl-2,5,5-trimethyl-1-hexanoic acid.

Synthesis of 2-t-butyl-2,5,5-trimethyl-1-hexanol Molecular weight 37.9 dispersed in 10 ml n-hexane.
1 to 0.569 g (15 mmol) of LiAlH _{4 of} 5
2-having a molecular weight of 214 dissolved in 0 ml of n-hexane
2.14 g (10 m) of crystals of t-butyl-2,5,5-trimethyl-1-hexanoic acid (SA13) (purity 92%).
mol) was added, and the mixture was stirred under reflux of n-hexane for 16 hours for reaction. After completion of the reaction, the reaction mixture is poured into water,
The aluminum hydroxide precipitate was filtered off. After distilling off n-hexane from the filtrate, Kugel distillation (93-125 ° C / to
rr) to obtain the desired alcohol (yield: 60
%).

Synthesis of alkyl ester 2-tert-butyl-2,5,5-trimethyl-1-
Hexanol 40 g (0.2 mol), phenothiazine (polymerization inhibitor) 400 mg, benzene (solvent) 200 m
1, 16.6 g (0.23 mol) of acrylic acid and 2.3 g of sulfuric acid (97% by weight: catalyst) were charged into a flask, and 8
The reaction was carried out while heating to 4 ° C and refluxing. At this time,
The reaction was carried out while removing a part of the solvent, and water produced thereby was azeotropically removed together with the solvent. After 4 hours, allow to cool to room temperature, and then add 200 ml of distilled water to the reaction product solution.
2 times with 200 ml of 10% sodium carbonate aqueous solution,
After further washing twice with 200 ml of distilled water in this order, removing water with magnesium sulfate, and then filtering,
The solvent was distilled off under reduced pressure to obtain a product (crude ester). Next, 50 g of the obtained product was dissolved in 150 ml of n-hexane, 2.5 g of activated carbon was added to the solution, and stirring was continued at room temperature for 4 hours. Then, after removing the activated carbon by filtration,
-Hexane was distilled off under reduced pressure to obtain a decolorized product (purified ester).

When the mass spectrum of the product thus obtained was analyzed, a peak of M ⁺ +1 was observed at a mass number of 255, so that the molecular weight of the product was found to be 254. In addition, according to the IR spectrum,
Absorption peak derived from C = O stretching vibration at 27 cm ^-1 , 1
Absorption peak derived from the 618cm ^-1 and 1633 cm ^-1 to C = C stretching vibration, further, 1055cm ^-1, 1194cm
^Since absorption peaks derived from C—O stretching vibration were observed at ⁻¹ and 1268 cm ⁻¹ , it was found that the product was an unsaturated ester. From the above analysis results, it was revealed that the desired alkyl ester of acrylic acid, which is the ester of alcohol and acrylic acid used, was quantitatively obtained by this ester reaction.

Example 2 270 g of a mixed solution of 54% by weight of sulfuric acid, 29% by weight of phosphoric acid and 7% by weight of water, and 2.3 g of cuprous oxide were charged into a magnetic stirring stainless autoclave (capacity: 1 liter). After replacing the air in the autoclave with carbon monoxide gas, the temperature is 25 ° C and the carbon monoxide gas pressure is 15 kg.
/ Cm ² G and stirring at a rotation speed of 1000 rpm for 3 hours to dissolve cuprous oxide (acidity = −8.1).
~ -7.5).

Subsequently, while maintaining the temperature and pressure, the olefin having 8 carbon atoms [diisobutylene (2,4,4-trimethyl-1-pentene: 70.9% by weight, 2,4,4
- trimethyl-2-pentene: 22.1% by weight, other C ₈ Oreifin: 7.0 wt%, Total: 100.0
% Weight)] 33.6 g was pumped into the autoclave over 90 minutes.

The carbon monoxide gas consumed along with the progress of the reaction has a gauge pressure of the carbon monoxide gas of 15 kg / cm ^2.
Replenished by keeping G.

After the supply of olefin was stopped, stirring was continued for another hour. After the reaction was completed, carbon monoxide remaining in the autoclave was removed, and the resulting reaction mixture was diluted with 3 times water. Extraction of this diluted solution was repeated three times with 200 ml of n-hexane. A crude carboxylic acid composition was obtained by combining the extracts and removing n-hexane from the extracts.

Next, this crude carboxylic acid composition was purified by distillation under reduced pressure to obtain 28 g of a carboxylic acid composition having a boiling point of 85 to 101 ° C./1 mmHg and a tertiary carboxylic acid having 9 carbon atoms as a main component. This carboxylic acid composition was used in Example 1.
A C ₉ alcohol composition was obtained by hydrogenation according to the method described in.

In Example 1, 40 g of the above C ₉ alcohol composition was used in place of 2-tert-butyl-2,5,5-trimethyl-1-hexanol, and the charged amount was 230 mg of phenothiazine and 23 g of acrylic acid. And 1.3 g of sulfuric acid, and the reaction and activated carbon treatment were carried out in the same manner as in Example 1 except that the reaction solvent was changed from benzene to n-hexane and the reaction temperature was 73 ° C. to obtain a predetermined product.

The structure of this product was confirmed by mass spectrum analysis and IR analysis in the same manner as in Example 1. The mass spectrum chart shows acrylic acid and C ₉
Mass number 1 corresponding to protonated molecular ion MH ⁺ corresponding to the molecular weight of alcohol ester (molecular weight: 198)
A peak of 99 and a peak of mass number 127 corresponding to the C ₉ alkyl cation of the fragment were recognized. In addition, in the IR chart, C unique to the unsaturated ester was used.
= O stretch (1724 cm ^-1 ), C = C stretch (1618,
1633 cm ^-1 ) and CO stretching (1056,119
4,1271 cm ^-1 ) was observed.

From the above results, the esterification reaction between the C ₉ alcohol composition used and acrylic acid was quantitatively achieved, and the esterification reaction product was the acrylic acid alkyl ester of the present invention [acrylic acid in this case]. It was confirmed that the desired acrylic acid ester composition [that is, an example of the (meth) acrylic acid ester composition of the present invention] containing the above-mentioned highly branched C ₉ alkyl ester] as a main component.

Example 3 In Example 1, 2-tert-butyl-2,5,5
5.0 g of the C ₉ alcohol composition obtained in Example 2 was used instead of -trimethyl-1-hexanol, and the charged amount was phenothiazine 32 mg and methacrylic acid 3.5.
g and sulfuric acid 0.22 g, and the reaction solvent was benzene to n
Reaction and activated carbon treatment were carried out in the same manner as in Example 1 except that 50 ml of hexane was used, the reaction temperature was 72 ° C., and the reaction time was 10 hours, to obtain the desired product.

The structure of this product was confirmed by mass spectrum analysis and IR analysis in the same manner as in Example 1. The mass spectrum chart shows methacrylic acid and C
Corresponding to the molecular weight of the ester of ₉ alcohol (molecular weight: 198), a peak of mass number 213 corresponding to protonated molecular ion MH ⁺ and a peak of mass number 127 corresponding to C ₉ alkyl cation of the fragment were observed.
In the IR chart, C = O stretching (1722 cm ^-1 ) and C = C stretching (1638) peculiar to the unsaturated ester are shown.
cm ^-1) and C-O stretch (1163cm ^-1) absorption such as was observed, et al.

From the above results, the esterification reaction between the C ₉ alcohol composition used and methacrylic acid was quantitatively achieved, and the esterification reaction product was the methacrylic acid alkyl ester of the present invention [in this case, methacrylic acid]. High branch C
It was confirmed that the desired methacrylic acid ester composition containing [ ₉ alkyl ester] as a main component [that is, an example of the (meth) acrylic acid ester composition of the present invention].

Example 4 In Example 2, an olefin having 12 carbon atoms was used as a main component instead of the olefin having 8 carbon atoms [IP162
0, olefin mixture, manufactured by Idemitsu Petrochemical Co., Ltd., C ₁₁ or less olein: 9.1% by weight, C ₁₂ olefin: 8
6.4% by weight, C ₁₃ or higher olefin: 4.5% by weight,
A crude carboxylic acid composition was obtained in the same manner except that (total: 100% by weight) was used. Then, this crude carboxylic acid composition is purified by distillation under reduced pressure, and has a boiling point of 119 to 127 ° C./1.
50.7 g of a carboxylic acid composition containing a tertiary carboxylic acid having 13 carbon atoms as a main component was obtained in mmHg. This carboxylic acid composition was hydrogenated according to the method described in Example 1 to obtain a C ₁₃ alcohol composition.

A C ₁₃ alcohol composition was obtained by hydrogenating the carboxylic acid composition containing a C ₁₃ tertiary carboxylic acid as a main component according to the method described in Example 1.

In Example 1, 40 g of the above C ₁₃ alcohol composition was used in place of 2-tert-butyl-2,5,5-trimethyl-1-hexanol, and the charged amount was 400 mg of phenothiazine and 16% of acrylic acid. .6
g and sulfuric acid 2.3 g were reacted and treated with activated carbon in the same manner as in Example 1 to obtain a predetermined product.

The structure of this product was confirmed by mass spectrum analysis and IR analysis in the same manner as in Example 1. The mass spectrum chart shows acrylic acid and C ₁₃
Mass number 2 corresponding to protonated molecular ion MH ⁺ corresponding to the molecular weight of alcohol ester (molecular weight: 254)
55 peaks and a mass number 183 peak corresponding to the C ₁₃ alkyl cation of the fragment were observed. In addition, in the IR chart, C unique to the unsaturated ester was used.
= O stretching (1727 cm ^-1 ), C = C stretching (1618,
1633 cm ^-1 ) and CO stretching (1055,119
4,1268 cm ^-1 ) and the like were observed.

From the above results, the esterification reaction between the C ₁₃ alcohol composition used and acrylic acid was quantitatively achieved, and the esterification reaction product was the acrylic acid alkyl ester of the present invention (in this case, acrylic acid). It was confirmed that the desired acrylic acid ester composition [an example of the (meth) acrylic acid ester composition of the present invention] containing the [highly branched C ₁₃ alkyl ester of] as the main component was obtained.

Examples 5 and 6 and Comparative Examples 1 to 6 Table 1 shows the composition of the acrylate ester having the C ₉ alkyl group as an alcohol residue (abbreviated as C9-A) obtained in Example 2. Trimethylolpropane triacrylate (TMP) as a curing agent at the stated blending ratio (parts by weight)
It is abbreviated as -3A. ), Irgac as a photopolymerization initiator
Ure 184 (manufactured by Ciba Geigy) was blended to prepare a liquid curable resin composition (an example of the curable resin composition of the present invention, which corresponds to Examples 5 and 6).

On the other hand, as a comparative example, a commercially available 2-ethylhexyl acrylate (abbreviated as 2EHA), which is a conventional acrylic ester having a low degree of branching, is used in place of the above acrylic ester composition (C9-A). Alternatively, isooctyl acrylate (abbreviated as IOA) is blended at the blending ratios shown in Table 1, respectively, and two conventional liquid curable resin compositions having different compositions (corresponding to Comparative Examples 1 to 4). Stuff) was prepared. Also, as another comparative example,
A liquid curable resin composition (which can be regarded as a conventional type and corresponds to Comparative Examples 5 and 6) was also prepared by mixing the above TMP-3A and Irgacure 184 in a mixing ratio shown in Table 1.

Next, about 1 ml of each of these curable resin compositions was placed on a Teflon board, and ultraviolet rays were applied thereto.
Each of the light amounts shown in Table 1 was irradiated and cured.

Table 1 shows the degree of cure of the resin, the specific gravity of the cured product, the specific gravity of the composition (liquid) before curing, and the shrinkage rate of the volume of the composition due to curing at that time. The volume contraction rate was calculated by the ratio of specific gravities before and after curing.

From the results shown in Table 1, comparing the cases of the same amount of light, it can be seen that the curable resin composition of the present invention containing C9-A obviously has a smaller volume shrinkage rate due to curing than the conventional one. Recognize.

[0092]

[Table 1] a) 80 mJ / cm ² × back, front × 1 or 2 times b) △ tack remains d) 23 ° C e) 15 ° C ○ Fingerprinting ◎ Complete curing

[0093]

EFFECTS OF THE INVENTION According to the present invention, it is not only useful as a raw material (monomer, comonomer, etc.) for producing a novel polymer or oligomer, but particularly used as a monomer component or a comonomer component of a curable resin or a curable resin composition. It is possible to expect various new or useful functions and properties such as effective suppression of volume shrinkage during polymerization and curing, but it has a structure with a sufficiently large degree of branching and steric hindrance. It is possible to provide various new (meth) acrylic acid esters which are esters of alkyl groups having a large

Further, according to the present invention, it is possible to provide not only the above-mentioned individual compounds of the novel (meth) acrylic acid alkyl ester but also a mixture of the alkyl ester or a composition containing the ester as a main component. .

Furthermore, according to the present invention, it is possible to provide a composition having various compositions containing the ester, which takes advantage of the characteristics peculiar to the (meth) acrylic acid ester of the present invention. Among them, particularly preferable applications As an example, the volume shrinkage during polymerization and curing is small, the adhesiveness between the cured resin film and its substrate is excellent, and the resin material has excellent performance such as easy precision design of the size or shape of the resin material. It is possible to provide a curable resin composed of an ester and a curable resin composition containing the ester as a main raw material or an additive or an improver.

The present invention also provides a method for industrially producing the above-mentioned (meth) acrylic acid ester (a single compound, a mixture, or a composition containing this as a main component) of the present invention in an industrially advantageous manner. it can.

Claims (5)

[Claims] 1. The following general formula [I]: (However, R ¹ , R ² and R ³ in the formula [I] have 1 to 1 carbon atoms.
The 15 alkyl groups may be the same or different from each other, and R ⁴ is a hydrogen atom or a methyl group. ) A new (meth) acrylic acid ester represented by: 2. A (meth) acrylic acid ester composition containing the (meth) acrylic acid ester according to claim 1 as a main component. 3. A curable resin comprising the (meth) acrylic acid ester according to claim 1. 4. A curable resin composition containing the (meth) acrylic acid ester according to claim 1. 5. The following general formula [II]: (However, R ¹ , R ² and R ³ in the formula [I] have 1 to 1 carbon atoms.
The 15 alkyl groups may be the same or different from each other. ) The following general formula [III] obtained by hydrogenating a tertiary carboxylic acid (However, R ¹ , R ² and R ³ in the formula [III] have the same meanings as described above.) The esterification reaction of the alcohol represented by methacrylic acid and / or acrylic acid. Item 2. A method for producing a (meth) acrylic acid ester according to Item 1.