JPH09309905A - Resin composition curable with actinic radiation - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make a coating, a film, and a molded roduct to be in a favorable state and favorably transparent and to improve surface properties and mechanical properties by adding a resin composition curable with actinic radiation and a specified aromatic polyester. SOLUTION: Out of resins curable with actinic radiation, such as acryllic type monomers or oligomers, radical-polymerizable compounds, and cationically polymerizable compounds, whose polymerization reaction is caused to proceed with infrared radiation, visible light, ultraviolet light, or electron radiation, one that can form a transparent homogenous mixed liquid with a side-chain- containing aromatic polyester in the presence or absence of an organic solvent in an amount of 100 pts.wt., a photoreaction initiator in an amount of 0.1 to 15 pts.wt., and an aromatic polyester that is soluble in a solvent and/or heat- meltable and wherein the main chain has an aromatic polyester structure, an aliphatic side chain having 2 or more carbon atoms and/or a fluorine-containing side chain and/or a dialkylsiloxane-containing side chain is attached to at least part of the aromatic ring in the main chain in an amount of 0.01 to 20 pts.wt. are used to obtain a resin composition curable with actinic radiation.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an active energy ray curable resin composition comprising an active energy ray curable resin and an aromatic polyester, which is useful in the fields of coating film, coating material, molding material and the like. It is about.

[0002]

2. Description of the Related Art An active energy ray curable resin is widely used as a coating material, a coating material, a sealing material, etc. because of its short curing time and good working efficiency. With the recent advancement of industries including the fields of electronics, electricity, automobiles, and construction, the required properties for active energy ray-curable resins are increasing.

In order to deal with them, for example, it has been considered to use an active energy ray curable resin by blending it with other organic molecules or polymers. In particular, improving the surface hardness of the active energy ray-curable resin, improving the surface characteristics when used in a coating film or coating, particularly improving the surface to have water repellency or oil repellency, etc. It is a big issue.

Conventionally, regarding the addition of a modifier for improving the surface characteristics of an active energy ray-curable resin, for example,
A low molecular weight material that is easy to handle is used as a surface modifier, but problems such as deterioration of the obtained surface characteristics due to aging and deterioration of mechanical properties of active energy ray-curable resin due to blending of low molecular weight compounds are problems. Has become.

On the other hand, blending with a thermoplastic polymer has also been studied in order to improve the surface characteristics and mechanical properties of the active energy ray-curable resin. However, thermoplastic polymers generally do not have good compatibility with active energy ray-curable resins, and phase separation and aggregation are likely to occur during the curing process. Therefore, a transparent composite having a finely dispersed state or an adhered interface is used. Is often difficult to obtain.

For example, a melted liquid crystalline aromatic polyester, which is known as a thermoplastic polymer having excellent mechanical properties, has extremely poor solvent solubility and has a strong self-aggregating property, so that it is forcibly blended. Also in the case where the dispersed particle size is large,
In addition, only a blend having poor interface adhesion was obtained, and a good composite with an active energy ray curable resin was not obtained.

[0007]

The problem to be solved by the present invention is that it has a good morphology and transparency as a coating film or film as a cured product or a molded product, and has a high contact angle with water and a low surface. It is an object of the present invention to provide an active energy ray-curable resin composition having excellent surface characteristics such as free energy and surface hardness and mechanical characteristics.

[0008]

[Means for Solving the Problems] The inventors of the present invention have been engaged in intensive research to solve the problems, and particularly as a thermoplastic polymer, the main chain has an aromatic polyester structure and the main chain aromatic ring An active energy-ray curable resin composition comprising an aromatic polyester having a side chain in a solvent-soluble and / or heat-meltable or melted liquid crystallinity and an active energy-curable resin has excellent performance. The present invention has been completed and the present invention has been completed.

That is, in the present invention, 100 parts by weight of the active energy ray curable resin, the main chain has an aromatic polyester structure, and at least a part of the aromatic ring in the main chain has a side chain having 2 or more carbon atoms. An active energy ray curable resin composition comprising 0.01 to 20 parts by weight of an aromatic polyester having solvent solubility and / or heat melting property, which is bonded.

In the present invention, the aromatic polyester used is
At least a part of the side chain of the aromatic polyester is an aliphatic side chain, and an active energy-ray curable resin composition, and at least a part of the side chain of the aromatic polyester is a fluorine-containing side chain. An active energy ray curable resin composition characterized by the above, or an active energy ray curable resin composition characterized in that at least a part of the side chain of the aromatic polyester is a dialkylsiloxane-containing side chain. .

The present invention also provides an active energy ray curable resin composition characterized in that the aromatic polyester to be used is one in which the side chain of the aromatic polyester has a branched structure, and the aromatic polyester to be used. An active energy ray curable resin composition having a main chain having a wholly aromatic polyester structure is included. The present invention also includes an active energy ray-curable resin composition in which the aromatic polyester used has a molten liquid crystallinity.

In the present invention, 100 parts by weight of the active energy ray curable resin is further used, and further, the aromatic polyester used has the above-mentioned structure, the main chain has an aromatic polyester structure, and at least one of the main chains is present. 0.01 to 20 parts by weight of a solvent-soluble and / or heat-meltable aromatic polyester in which a side chain having 2 or more carbon atoms is bonded to a part of the aromatic ring, and a photoinitiator 0.1 to 15 An active energy ray-curable resin composition containing parts by weight is included.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The active energy ray-curable resin used in the present invention may be any one that can undergo a polymerization reaction by irradiation with infrared rays, visible rays, ultraviolet rays or electron beams, and examples thereof include polyester acrylate. Acrylic monomers and oligomers such as urethane, acrylate, polyether acrylate, epoxy acrylate, polybutadiene acrylate, silicone acrylate, alkyl acrylate, etc.

Commercially available active energy rays such as liquid polybutadiene compounds, unsaturated polyester compounds, radical polymerizable compounds such as polyene-polythiol compounds, aminoalkyd resins, cationic polymerizable compounds such as epoxy type and vinyl ether type compounds. Curable resins and the like can be mentioned.

As these active energy ray-curable resins, preferably, a homogeneous liquid mixture with the side chain-containing aromatic polyester in the present invention can be prepared in the presence of an organic solvent or alone without an organic solvent. It is preferable that it is a transparent homogeneous mixed liquid.

In order to photopolymerize the active energy ray curable resin, it is usually preferable to use a photoreaction initiator in combination. The photoreaction initiator used in the present invention includes active energy
A radical-type or cation-type photoreaction initiator which is usually used in the radiation curable resin is used. It is preferable that the coexistence of a photoreaction initiator in the active energy ray curable resin system does not induce phase separation of the aromatic polyester.

The addition amount of the photoreaction initiator cannot be unconditionally specified because it varies depending on the type of the reaction initiator used and the type of the active energy ray curable resin, but it is preferably the active energy ray curable resin. 0.1 to 15 parts by weight is used for 100 parts by weight. If it is less than 0.1 part by weight, the reaction of the reactive monomer is often insufficient,
If it exceeds 15 parts by weight, the physical properties of the composite may be deteriorated.

The aromatic polyester used in the present invention has a main chain having an aromatic polyester structure, and at least a part of aromatic rings in the main chain has an aliphatic side chain and / or a fluorine-containing side chain and / or a dialkyl. It is essential that the siloxane-containing side chain is bound, and it is necessary that it has solvent solubility and / or heat melting property.

The main chain structure of the aromatic polyester used in the present invention includes a wholly aromatic polyester structure consisting only of an aromatic ring and an ester bond, and an aromatic polyester structure containing an aliphatic chain as a part of the main chain, Further, those having an aromatic polyester structure showing a melted liquid crystallinity only in the main chain are also included. Here, as the side chain substituted or unsubstituted main chain aromatic ring, various aromatic rings such as a phenylene ring, a biphenylene ring and a naphthalene ring are used.

The side chain of the aromatic polyester used in the present invention is preferably an aliphatic side chain having 2 or more carbon atoms, particularly preferably 4 or more carbon atoms, a fluorine-containing side chain or a dialkylsiloxane-containing side chain. Those having a chain structure or a branched structure are used. When the side chain has only one carbon atom or has no side chain at all, it does not have solvent solubility and / or heat meltability, or has fine dispersibility in an active energy ray-curable resin and an interface. Adhesion is not good and composite with thermosetting resin is not effectively achieved.

Aromatic polyesters having two or more carbon atoms and having neither solvent solubility in an organic solvent nor heat melting property are not used in the present invention. However, even if it partially contains an aromatic ring having a side chain carbon number of 1 or an aromatic ring having no side chain, by combining with an aromatic polyester having various side chains of 2 or more carbon atoms in the copolymer, Those which have achieved solubility in a solvent or thermal melting property can be used in the present invention.

The aliphatic side chain of the aromatic polyester used in the present invention has 2 or more carbon atoms, preferably 2 to 20 carbon atoms, and has a linear or branched structure. The aliphatic side chain may be substituted on all the aromatic rings in the main chain, or may be substituted on a part of the aromatic rings in the main chain. The number of side chains substituted by one aromatic ring is one or two or more.

As the aliphatic side chain having a branched structure, one or a plurality of secondary or tertiary carbons are contained in the side chain.
Those having at the end or in the middle are used, and specifically,
One side chain is branched into two chains, three chains, etc.,
Examples thereof include those having an isopropyl group or a tert-butyl group at the end of the aliphatic side chain.

The aliphatic side chain having a branched structure is effective in improving the surface characteristics of the active energy ray curable resin composition. Further, also in the following fluorine-containing side chains and dialkylsiloxane-containing side chains, those having a similar branched structure can be effectively used.

The fluorine-containing side chain of the aromatic polyester used in the present invention has 2 or more carbon atoms, preferably 2 to 30 carbon atoms, and at least a part of hydrogen in the side chain is substituted with fluorine. Those having a branched structure in which the terminal side of the side chain is fluorine-substituted and / or the fluorine-containing side chain has a branched structure are preferred. Examples of the terminal group having a fluorine-containing group at the terminal side of the side chain include those having the following structures.

-X (CH ₂ ) _n (CF ₂ ) _m F, or -X
_{(CH 2) n (CF 2} ) m H ( in the formula, n represents an integer of 1 to 10, m is an integer of 1 to 20,
X represents an ether bond or an ester bond. )

The fluorine-containing side chain may be substituted on all the aromatic rings in the main chain, or may be substituted on a part of the aromatic rings in the main chain. The number of side chains substituted by one aromatic ring is one or two or more. Those having such a fluorine-containing side chain are effective in improving the surface characteristics of the active energy ray-curable resin composition.

Further, the aromatic polyester in the present invention includes those having an aliphatic side chain together with a fluorine-containing side chain, and for example, a fluorine-containing side chain is bonded to a part of the aromatic ring in the main chain. , Those in which an aliphatic side chain is bonded to a part or all of the remaining aromatic ring in the main chain.

The ratio of the fluorine-containing side chain to the aliphatic side chain varies depending on the length of each side chain and cannot be specified unconditionally, but (number of fluorine-containing side chains / number of aliphatic side chains) = 0.05 to 1 Those in the range of are preferably used. When the ratio is less than 0.05, the effect of the fluorine-containing side chain is small, and when it is 1 or more, the performance is often the same as that of the case of using the fluorine-containing side chain alone, and the effect of using the aliphatic side chain together is weakened.

As the aromatic polyester used in the present invention, those having a side chain containing a dialkylsiloxane structure include those having a dialkylsiloxane structure in at least a part of the side chain, and the number of siloxanes is 2 or more. It is preferable that the number of siloxanes is 2 to 100.

Further, it is more preferable that the terminal side of the side chain has a dialkylsiloxane structure and / or the side chain containing the dialkylsiloxane has a branched structure. Examples of those having a dialkylsiloxane structure on the terminal side of the side chain include those having the following structures.

-X (CH ₂ ) _n (Si (R) ₂ O) _m R (where n is an integer of 1 or more, m is an integer of 2 to 100, X
Is an ether or ester bond, R is 1 or 2 carbon atoms
Represents an alkyl group. )

The dialkylsiloxane-containing side chain may be substituted with all the aromatic rings in the main chain, or may be substituted with a part of the aromatic rings in the main chain. The number of side chains substituted by one aromatic ring is one or two or more. Those having such a dialkylsiloxane-containing side chain are effective in improving the surface characteristics of the active energy ray-curable resin composition.

Further, the aromatic polyester in the present invention includes those having an aliphatic side chain and / or a fluorine-containing side chain together with a dialkylsiloxane-containing side chain. For example, a part of the aromatic ring in the main chain has a dialkyl group. Examples thereof include those having a siloxane-containing side chain bonded thereto and having an aliphatic side chain and / or a fluorine-containing side chain bonded to a part or all of the remaining aromatic ring in the main chain.

The ratio of the dialkylsiloxane-containing side chain to the other side chain varies depending on the length of each side chain and cannot be unconditionally defined, but (number of dialkylsiloxane-containing side chains / number of other side chains) = 0. Those in the range of 001 to 1 are preferably used. Here, if the ratio is less than 0.001, the effect of the dialkylsiloxane-containing side chain is small, and if the ratio is 1 or more, the effect of using other side chains together is small.

In the present invention, various side chains of the aliphatic side chain, the fluorine-containing side chain, and the dialkylsiloxane-containing side chain and the main chain may be used, but the ether bond (--O With respect to the bond between the main chain aromatic ring and the side chain by-) or an ester bond (-COO-), the side chain can be easily introduced and is preferably used. In the present invention, the carbon contained in the above-mentioned bond connecting the main chain and the side chain is not included in the carbon number of the side chain.

Specific examples of the aromatic polyester having an aliphatic side chain and / or a fluorine-containing side chain and / or a dialkylsiloxane-containing side chain according to the present invention include aromatic compounds having one or more such side chains. Aromatic polyesters obtained by using dicarboxylic acid and side chain-unsubstituted aromatic diol as a monomer, or conversely, side chain unsubstituted aromatic dicarboxylic acid and aromatic diol having the above side chain as monomers The aromatic polyester obtained, an aromatic polyester obtained by using both monomers having the above-mentioned side chains, and further an aromatic polyester having a hydroxycarboxylic acid having a side chain as a monomer, and the like.

As the aromatic polyester in the present invention, in addition to a homopolymer having a fixed repeating chemical structural unit, plural kinds of aromatic monomers may be used, or a main chain may have a bonding property such as a paraphenylene ring or a metaphenylene ring. Also included are copolymers obtained using different aromatic rings.

For example, in the case where the main chain contains an aliphatic side chain or a metaphenylene ring, surface characteristics, thermal characteristics, solvent solubility, etc. can be controlled more widely, and a high molecular weight aromatic polyester can be obtained. If possible, the use of the meta isomer monomer is excellent in cost and production yield.

Further, as one kind of such an aromatic polyester copolymer, an amide bond or an ether bond is formed in the main chain ester bond.
It is also possible to use a material in which a tell bond or the like is partially introduced. Further, it may be obtained by using a copolymer having a plurality of kinds of aliphatic side chains and / or fluorine-containing side chains and / or dialkylsiloxane-containing side chains having different side chains having different lengths or structures, and an unsubstituted monomer together. Also used are copolymers.

In any of the copolymers, the copolymerization ratio and block property, and the copolymerization ratio of the main chain portion and the side chain portion are not limited as long as they have solvent solubility and / or heat melting property. Copolymerization in the main chain and / or side chain as described above controls and improves surface characteristics, mechanical characteristics, solvent solubility, melting temperature and liquid crystallinity of the aromatic polyester itself, and also active energy ray curing. It is possible to improve the miscibility with the mold resin and is effective in improving the surface characteristics and mechanical characteristics of the resulting active energy ray-curable resin composition.

Aromatic polyesters having neither solvent solubility in an organic solvent nor heat melting property in the present invention do not belong to the present invention. Further, those having no solvent solubility are difficult to form a composite with an active energy ray-curable resin using a solution, and therefore, in the surface characteristics and mechanical characteristics of the obtained active energy ray-curable resin composition. Often inferior.

On the other hand, a resin having both solubility in an organic solvent and thermal melting property is preferable in terms of blending property with an active energy ray-curable resin, and a compound exhibiting liquid crystallinity during melting is capable of controlling orientation. Therefore, it is also excellent in improving the mechanical properties of the active energy ray-curable resin composition.

The amount of the aromatic polyester used in the present invention is preferably 0.01 to 20 parts by weight, particularly preferably 0.05 to 10 parts by weight, based on 100 parts by weight of the active energy ray-curable resin. It is a department. If it is less than 0.01 parts by weight, the blending effect of the aromatic polyester will be small, and if it is more than 20 parts by weight, the curability of the active energy ray curable resin may be deteriorated.

The present invention is characterized in that the effect of modifying the surface properties and the like can be obtained by adding a small amount of aromatic polyester, and as shown in the examples, it is only 0.5% by weight or less. The composite with the aromatic polyester can improve the surface characteristics such as high contact angle with water and low surface free energy, or high surface hardness.

Further, in general, when a large amount of a thermoplastic polymer is blended with an active energy ray-curable resin, the transparency of the blended product is often lowered, but the addition of a small amount as in the present invention causes a decrease in transparency. Has the feature of being very small, if any. Active energy in the present invention
As a method for preparing an active energy ray curable resin composition containing a ray curable resin and an aromatic polyester, various methods are possible depending on the properties of both resins to be used and are not particularly limited.

Specifically, a method of directly mixing the active energy ray-curable resin and the aromatic polyester, or a method of mixing one or both of them in a suitable organic solvent having solubility in both resins is mixed. Method, or a method of removing at least a part of the organic solvent after preparing the solution, a method of mixing with another dispersion promoter, and the like.

Various methods are available for obtaining a good coating film or molded product of the active energy ray-curable resin using the active energy ray-curable resin composition of the present invention. As an example, the above active energy ray curable resin composition or a solution obtained by dissolving the active energy ray curable resin composition in a solvent is prepared, and is applied or cast or injected onto a predetermined substrate or in a mold.

Then, conditions such as temperature, gas flow, and vacuum are selected, the solvent is removed as necessary, and active energy rays are irradiated to advance the curing reaction of the active energy ray curable resin. Examples thereof include a method of obtaining a coating film, a film, or a molded product having good physical properties.

Here, in addition to the photoreaction initiator, a reaction accelerator or other generally used physical property-improving agent, and a filler such as glass fiber are added to the active energy ray-curable resin in advance or in the middle thereof. This can be carried out within a range in which the aromatic polyester is not separated or precipitated from the system.

A cured product obtained by using the active energy ray-curable resin composition of the present invention has a good form and / or transparency as a coating film, a film or a molded article, and
Due to the effect that the aromatic polyester is concentrated on the surface of the coating film or the molded body when the coating film or film is formed or the active energy ray of the resin is cured, or the side chains of the aromatic polyester are aggregated on the surface. It has excellent surface properties such as high water contact angle and low surface free energy.

Aromatic polyester is finely dispersed in a resin cured product which has been cured into a molded article such as a coating film or a film by active energy rays, whereby a cured product of an active energy ray curable resin is obtained. It is possible to improve surface hardness and mechanical properties as compared with a single substance.

When a commercially available aromatic polyester having a melted liquid crystallinity represented by, for example, Vectra (produced by Ceranizu) is used in place of the aromatic polyester used in the present invention, the solvent solubility is improved. Since it does not have, and the dispersibility in the active energy ray-curable resin and the interfacial adhesion are poor even if it is blended by kneading forcibly, the composite with the excellent active energy ray-curable resin as in the present invention I can't get a body.

[0054]

The present invention will be further described with reference to examples.

(Production Example 1) 0.1 mol of pyromellitic dianhydride and 0.2 mol of 1-hexadecanol were stirred in a dry inert gas atmosphere and slowly heated to 150 ° C. for 45 minutes. Stir and hold. After cooling, 400 mL of acetone was added, and the mixture was stirred for 12 hours and then filtered. The filtered product was repeatedly washed with acetone with stirring, and then filtered to obtain a para-form dicarboxylic acid monomer into which two aliphatic side chains were introduced.

10 moles of thionyl chloride was added to 0.05 mole of the obtained monomer and the mixture was refluxed at 80 to 90 ° C. for 20 minutes, and then excess thionyl chloride was removed to obtain the chloride of the monomer. . While stirring vigorously a solution prepared by dissolving 0.04 mol of 4,4'-biphenol and triethylamine (2 times its equivalent) in 30 mL of tetrahydrofun, the monomer chloride equivalent to the amount of biphenol was dissolved in tetrahydrofuran. The dissolved solution was added dropwise.

After the solution became viscous and the reaction was completed, the solution was added to 500 mL of methanol to precipitate the polymer, which was then filtered, and the solvent and tetrahydrofuran solvent were added.
The polymer was repeatedly dissolved and reprecipitated, and finally washed with methanol and dried to obtain a polymer. By the above method,
An aromatic polyester A having two aliphatic side chains per repeating unit structure, in which a side chain of — (CH ₂ ) ₁₅ CH ₃ was bound to a main chain aromatic ring by an ester bond, was obtained (Polymer A). The obtained polymer-A was dissolved in chloroform.
Further, when heated to a temperature of 87 ° C. (Tm), it became a molten liquid crystal, and at 123 ° C. (Ti), it became an isotropic melt.

(Production Example 2) 0.1 mol of pyromellitic dianhydride and 0.2 mol of neopentyl alcohol were stirred in a dry inert gas atmosphere while slowly raising the temperature to 150 ° C. and stirring for 45 minutes. Held After cooling, 300 mL of a toluene / acetone mixed solution was added, and the mixture was stirred for 12 hours and then filtered. The filtrate was washed with hexane to obtain a para-dicarboxylic acid monomer having two aliphatic side chains.

To 0.05 mol of the obtained monomer, 4 times mol of thionyl chloride and 80 mL of tetrahydrofuran were added, and the mixture was refluxed at 80 to 90 ° C. for 20 minutes, and then the tetrahydrofuran and excess thionyl chloride were removed. Of chloride was obtained. 4,4'-biphenol 0.
While stirring strongly, a solution of 02 mol and twice its equivalent amount of triethylamine in 30 mL of tetrahydrofun,
A solution prepared by dissolving an equimolar amount of biphenol and a monomer chloride in tetrahydrofuran was added dropwise.

After the solution became viscous and the reaction was completed, the solution was added to 500 mL of methanol to precipitate a polymer, which was then filtered and the solvent was tetrahydrofuran and methanol.
The polymer was repeatedly dissolved and reprecipitated, and finally washed with methanol and dried to obtain a polymer. By the above method,
An aromatic polyester B having two aliphatic side chains per repeating unit structure in which a side chain of —CH ₂ C (CH ₃ ) ₃ was bonded to a main chain aromatic ring by an ester bond was obtained (Polymer B). The obtained polymer B was dissolved in chloroform and N-methylpyrrolidone. 250 ° C in heating
It became a molten liquid crystal at (Tm) and became an isotropic melt at 315 ° C. (Ti).

(Production Example 3) 0.1 mol of pyromellitic dianhydride and 0.2 of 6- (perfluoroethyl) hexanol
While stirring in a dry inert gas atmosphere, the moles were slowly heated to 150 ° C. and held for 45 minutes while stirring. After cooling,
450 mL of acetone / chloroform mixed solution was added, and the mixture was stirred for 12 hours and then filtered. The filtrate was washed with chloroform to obtain a para-dicarboxylic acid monomer having two fluorine-containing side chains.

To 0.05 mole of the obtained monomer, 10 times mole of thionyl chloride and 10 mL of tetrahydrofuran were added, and the mixture was refluxed for 20 minutes, and then tetrahydrofuran and excess thionyl chloride were removed to remove the chloride of the monomer. Obtained. While stirring vigorously a solution prepared by dissolving 0.02 mol of 4,4'-biphenol and twice its equivalent amount of triethylamine in 30 mL of tetrahydrofuran, the monomer chloride in an equimolar amount of biphenol was added to tetrahydrofuran. The solution dissolved in was added dropwise.

After the solution became viscous and the reaction was completed, the solution was added to 500 mL of methanol to precipitate a polymer, which was then filtered, and the solvent was mixed with tetrahydrofuran and methanol.
The polymer was repeatedly dissolved and reprecipitated, and finally washed with methanol and dried to obtain a polymer. By the above method,
_{- (CH 2) 6 (CF} 2) and the ₂ F side chain of bound to the main chain aromatic ring with ester bonds to give an aromatic polyester C with two fluorine-containing side chain per repeating unit structure (Polymer C ). The obtained polymer-C was dissolved in chloroform, acetone and N-methylpyrrolidone. In addition, when heated to a temperature of 114 ° C (Tm), it becomes a liquid crystal and becomes 155 ° C
It became an isotropic melt in i).

Production Example 4 0.1 mol of pyromellitic dianhydride and 0.2 mol of 1-pentanol were stirred in a dry inert gas atmosphere, and the temperature was slowly raised to 150 ° C. 6
It was kept stirring for 0 minutes. After cooling, 450 mL of toluene was added to recrystallize. The filtered product was washed with toluene several times to obtain a para-substituted aliphatic side chain-substituted monomer.

To 0.05 mol of the obtained monomer, 10-fold mol of thionyl chloride was added, and the mixture was refluxed at 80 to 90 ° C. for 60 minutes, and then excess thionyl chloride was removed to obtain a chloride of the monomer. On the other hand, pyromellitic dianhydride 0.
1 mole of a terminal alkylalkoxy - Le dimethylsiloxane oligomer - (X-22-170AX: manufactured by Shin-Etsu Chemical Co., Ltd.: chemical formula _{HO (CH 2) 10 (OSi} (CH 3)
₂ ) 0.2 mol of ₂₀ CH ₃ ) and a catalytic amount of dimethylformamide were slowly heated to 150 ° C. with stirring in a dry inert gas atmosphere, and the mixture was kept stirring for 60 minutes.

Monomers are mixtures of meta and para substitutions. After adding 10 times mol of thionyl chloride to 0.05 mol of the obtained monomer and refluxing the mixture at 80 to 90 ° C. for 60 minutes, excess thionyl chloride was removed to obtain a chloride of the monomer. 0.0002 mol of the dimethylsiloxane-containing side chain-substituted monomer chloride and 0.0198 mol of the para-substituted aliphatic side chain-substituted monomer chloride.
To a solution of 0.04 mol of 4,4'-biphenol and 30 mL of tetrahydrofuran was added 4 parts of biphenol.
Double volume of pyridine was added dropwise with vigorous stirring.

After the solution became viscous and the reaction was completed, the solution was added to 500 mL of methanol to precipitate the polymer, which was then filtered and the solvent was dissolved in tetrahydrofuran and methanol.
The polymer was repeatedly dissolved and reprecipitated, and finally washed with methanol and dried to obtain a polymer. By the above method,
_{- (CH 2) 10 (OSi} (CH 3) 2) and the side chain of the ₂₀ CH ₃ -
An aromatic polyester copolymer D having a side chain of (CH ₂ ) ₄ CH _{3 in} a ratio of 1:99 (side chain number ratio) was obtained. (Polymer D)

Here, both side chains are bonded to the main chain aromatic ring by an ester bond. The polymer-D obtained was soluble in chloroform and tetrahydrofuran. Further, it is melted at 150 ° C. (Tm) in heating by heating, and thereafter 150 to 26
It exhibited optical anisotropy under shear stress at 0 ° C.

(Production Example 5) 0.002 mol of dimethylsiloxane-containing side chain-substituted monomer chloride obtained by the same method as in Production Example 4 and para-substituted aliphatic side chain-substituted monomer chloride 0.018 mol of the product and 0.02 mol of 4,4'-biphenol were dissolved in 30 mL of tetrahydrofuran, and 4 times equivalent amount of pyridine of biphenol was added dropwise with vigorous stirring.

After the solution became viscous and the reaction was completed, the solution was added to 500 mL of methanol to precipitate the polymer, which was then filtered, and the solvent and tetrahydrofuran solvent were added.
The polymer was repeatedly dissolved and reprecipitated, and finally washed with methanol and dried to obtain a polymer.

By the above method,-(CH ₂ ) ₁₀ (OS
An aromatic polyester copolymer E (polymer E) having a side chain of i (CH ₃ ) ₂ ) ₂₀ CH _{3 and} a side chain of — (CH ₂ ) ₄ CH ₃ at a ratio of 10:90 (side chain number) is prepared. Obtained. Here, both side chains are bonded to the main chain aromatic ring by an ester bond. The obtained polymer-E was soluble in chloroform and tetrahydrofuran. Further, it melted at 130 ° C. (Tm) in heating at elevated temperature, and thereafter showed optical anisotropy under shear stress at 130 to 180 ° C.

Example 1 The polymer obtained in Production Example 1
A solution of 0.05 g of A dissolved in 4.95 g of chloroform and nonaethylene glycol diacrylate which is an active energy ray curable resin (Kyoeisha Chemical Co., Ltd. 9
10 g of EG-A) dissolved in 23 g of chloroform and 0 of 2-hydroxy-2-methyl-1-phenyl-propan-1-one (1173DAROCURE manufactured by Ciba-Gaigi Japan Co., Ltd.) which is a photoinitiator. .75 g
And were mixed to prepare a mixed solution.

Flow the resulting mixed solution onto a clean glass plate.
After rolling, evaporate the solvent at room temperature in a dark atmosphere and place it on a glass plate.
A cast film was obtained. UV curing device
CU04 Co., Ltd. UB044-5AM-4)
External radiation dose 200 mJ / cm ^Two, High pressure mercury lamp (160
W), UV curing under aluminum mirror condition, thickness 4
A 0 μm film was made. The resulting film is
Polymer to 100 parts by weight of reactive energy ray curable resin
It contains 0.5 parts by weight of A.

The obtained film is a contact angle measuring device
FACE contact angle meter manufactured by Washi Interface Science Co., Ltd.
Contact with water, diiodomethane, ethylene glycol
Calculate the surface free energy and the contact angle with water from the angle
Was. In addition, a turbidimeter (NDH-30 manufactured by Nippon Denshoku Co., Ltd.)
Haze of the film using a
Degree measuring device (manufactured by Shimadzu Corporation, Dynamic Ultra Fine)
The surface hardness of the film was measured using a small hardness meter.
As a result, the water contact angle was 96.1 degrees and the surface free energy
Is 34.0 mN / m, haze is 3.1, and surface hardness is
4.9 gf / μm ^TwoMet.

Examples 2 and 3 In the preparation of a chloroform solution of Polymer-A, 0.5 g of Polymer-A was dissolved in 19.5 g of chloroform (Example 2), or 0.02 g of Polymer-A was dissolved. Example 1 except that it was dissolved in 1.98 g of chloroform (Example 3).
An ultraviolet curable film having a thickness of 40 μm was obtained in the same manner as in. The obtained film is an active energy ray curable resin 1
5 parts by weight of Polymer-A with respect to 00 parts by weight (Example 2)
Alternatively, it contains 0.2 parts by weight (Example 3). Table 1 shows the results obtained by measuring the physical properties of the film in the same manner as in Example 1.

(Examples 4 and 5) Example 4 was carried out in the same manner as in Example 1 except that the polymer B obtained in Production Example 2 was used in place of the polymer A, and in Example 5 By the same method as in Example 2, an active energy ray-curable resin film having a thickness of 40 μm was obtained. The obtained film contains 0.5 parts by weight of Polymer B in Example 4 and 5 parts in Example 5 with respect to 100 parts by weight of active energy ray-curable resin.
It includes parts by weight. Example 1 for measuring the physical properties of the film
Table 1 shows the results obtained by the same method.

Example 6 An active energy ray curable resin film having a thickness of 40 μm was prepared in the same manner as in Example 1 except that the polymer C obtained in Production Example 3 was used instead of the polymer A. Got The obtained film was obtained by adding Polymer C to 100 parts by weight of active energy ray-curable resin.
It contains 5 parts by weight. Table 1 shows the results obtained by measuring the physical properties of the film in the same manner as in Example 1.

(Examples 7 to 9) In preparing a chloroform solution of Polymer-C, 0.005 g of Polymer-C was dissolved in 0.995 g of chloroform (Example 7).
Or 0.02 g of Polymer-C is added to chloroform 1.98.
4 g in the same manner as in Example 6 except that 0.1 g of Polymer-C was dissolved in 9.9 g of chloroform (Example 9).
An ultraviolet curable film of 0 μm was obtained.

The obtained film contained 0.05 parts by weight of Polymer C (Example 7), 0.2 parts by weight (Example 8) or 1.0 part by weight of 100 parts by weight of the active energy ray curable resin. It includes parts by weight (Example 9). Table 1 shows the results obtained by measuring the physical properties of the film in the same manner as in Example 1.

Example 10 An active energy ray curable resin film having a thickness of 40 μm was prepared in the same manner as in Example 8 except that the polymer D obtained in Production Example 4 was used instead of the polymer C. Obtained. The obtained film had a polymer D content of 0.1 parts by weight per 100 parts by weight of the active energy ray-curable resin.
It contains 2 parts by weight. As a result of measuring the physical properties of the film obtained by the same method as in Example 1, the water contact angle was 98.5.
The surface free energy was 30.2 mN / m and the haze was 1.0.

Example 11 Example 1 was repeated except that 0.005 g of Polymer D was dissolved in 0.995 g of chloroform in the preparation of a chloroform solution of Polymer D.
An ultraviolet curable film having a thickness of 40 μm was obtained in the same manner as in 0. The obtained film is an active energy ray curable resin 1
It contains 0.05 parts by weight of Polymer-C with respect to 00 parts by weight. As a result of measuring the physical properties of the film obtained by the same method as in Example 1, the water contact angle was 93.3 degrees, the surface free energy was 31.2 mN / m, and the haze was 0.1.

Example 12 An active energy ray curable resin film having a thickness of 40 μm was prepared in the same manner as in Example 11 except that the polymer E obtained in Production Example 5 was used in place of the polymer D. Obtained. The obtained film contains 0.05 part by weight of Polymer E per 100 parts by weight of the active energy ray-curable resin. As a result of measuring the physical properties of the film obtained by the same method as in Example 1, the water contact angle was 9
The surface free energy was 5.8 degrees, 37.8 mN / m, and the haze was 0.1.

Comparative Example 1 An active energy ray curable resin film having a thickness of 40 μm was obtained in the same manner as in Example 1 except that the chloroform solution of polymer A was not used.
The obtained film is an active energy ray curable resin 100.
It does not contain aromatic polyester with respect to parts by weight. Table 1 shows the results obtained by measuring the physical properties of the film in the same manner as in Example 1.

(Comparative Example 2) A commercially available aromatic polyester having a liquid crystallinity (trade name: Idemitsu LCP200E, manufactured by Idemitsu Petrochemical Co., Ltd.) was used instead of the polymer A, and a similar active energy ray curable resin was used. An attempt was made to prepare a composition, but the solvent solubility of the aromatic polyester was extremely poor, and a homogeneous composition could not be prepared.

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[Table 1]

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INDUSTRIAL APPLICABILITY The present invention has, as a cured product, a good form and transparency as a coating film, a film or a molded article, and
An active energy ray-curable resin composition having excellent surface characteristics such as high contact angle with water, low surface free energy, and surface hardness and mechanical characteristics can be provided.

Claims (8)

[Claims] 1. An active energy ray curable resin 100 parts by weight, a main chain having an aromatic polyester structure, and a side chain having 2 or more carbon atoms bonded to at least a part of aromatic rings in the main chain. An active energy ray curable resin composition containing 0.01 to 20 parts by weight of an aromatic polyester having solvent solubility and / or heat melting property. 2. The active energy ray curable resin composition according to claim 1, wherein at least a part of a side chain of the aromatic polyester is an aliphatic side chain. 3. The aromatic polyester is characterized in that at least a part of its side chains is a fluorine-containing side chain.
The active energy ray-curable resin composition as described in 1. 4. The active energy ray curable resin composition according to claim 1, wherein at least a part of the side chain of the aromatic polyester is a dialkylsiloxane-containing side chain. 5. The active energy ray curable resin composition according to claim 1, wherein the side chain of the aromatic polyester has a branched structure. 6. The main chain of the aromatic polyester has a wholly aromatic polyester structure.
The active energy ray-curable resin composition according to any one of 1. 7. The active energy ray curable resin composition according to any one of claims 1 to 6, wherein the aromatic polyester has a molten liquid crystallinity. 8. The active energy ray-curable resin composition according to any one of claims 1 to 7,
100 parts by weight of the linear curable resin, the main chain has an aromatic polyester structure, and at least a part of the aromatic ring in the main chain has a side chain of 2 or more carbon atoms bonded, solvent solubility and / or Aromatic polyester having heat melting property 0.01 to 20
An active energy ray curable resin composition comprising 0.1 part by weight and 0.1 to 15 parts by weight of a photoreaction initiator.