TWI542604B - Novel polymer - Google Patents

Description

Novel polymer

The present invention relates to a novel polymer excellent in heat resistance.

In the past, a polymer having a photopolymerizable property, which is excellent in heat resistance, has been proposed, for example, a polymer obtained by polymerizing a monomer component containing maleimide (for example, refer to JP-A-2003-201316). A polymer obtained by polymerizing an ether dimer of a compound of a specific structure, that is, a 2-(hydroxyalkyl) acrylate (for example, refer to JP-A-2004-300203).

However, the fact that the polymers are thermally decomposed upon heating in the film or film forming step and the decomposition gas is generated is quite remarkable. For example, when such a polymer is used as a photosensitive resin for producing a liquid crystal display or a printed wiring board, the decomposition product generated during heating in the manufacturing step may contaminate the heating furnace, or the decomposition product may contaminate the liquid crystal or the substrate and be electrically Insulation is reduced, etc.

Further, maleimide, styrene, and a polymer having an acid group have been proposed (for example, refer to Japanese Laid-Open Patent Publication No. 2002-30119). However, such a polymer has a problem that the dissolution rate of an organic solvent or an alkali is slow. Therefore, there is a demand for a polymer which is improved in heat resistance and which is easy to prepare a resin composition, and which can improve developability when used as a photosensitive resin.

Accordingly, it is an object of the present invention to provide a polymer which is excellent in heat resistance Further, it is possible to reduce the gas generated during heating, and it has a high dissolution rate for an organic solvent or an alkali, and is excellent in alkali developability.

The present inventors have made an effort to solve the above problems. As a result, it has been found that an N-substituted maleimide and/or a compound of a specific structure, that is, an ether dimer of 2-(hydroxyalkyl)acrylate, vinyltoluene, and a monomer having an acid group are essential components. The copolymerized polymer can solve this problem in one fell swoop, and the present invention is completed in 焉.

That is, the present invention is characterized in that a compound represented by N-substituted maleimide and/or a compound represented by the following formula (1), vinyl toluene, and a monomer having an acid group are copolymerized as an essential component. Made of polymer.

(In the formula (1), R & lt ¹ and R ² each independently represents a hydrogen atom or a substituent having a carbon number of the hydrocarbon group of 1 to 25).

Fig. 1 is a view showing the state of a substrate after alkali development in Example 3.

Fig. 2 is a view showing a state of a substrate after alkali development in Comparative Example 3.

The above values and the following are included in the description of this manual. That is, "above" means not less than (the value and the value above).

The polymer of the present invention is an N-substituted maleimide and/or a compound represented by the following formula (1) (hereinafter sometimes referred to as "ether dimer"), vinyl toluene, and an acid. A monomer obtained by copolymerizing a monomer as an essential component.

(In the formula (1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.)

Therefore, the photosensitive resin composition using the polymer of the present invention is extremely excellent in heat resistance and transparency. It is presumed that the reason is that the heat resistance is greatly improved and the thermal decomposition is suppressed (the heat decomposition resistance is improved by the main chain ring structure formed by polymerizing the N-substituted maleimide and the ether dimer, and the vinyl toluene structure. ) caused.

Moreover, the inventors have found that the heat resistance of the photosensitive resin is likely to be thermally decomposed if there is an ester bond in the polymer. Therefore, in the polymer of the present invention, it is preferred that the structure has substantially no ester bond. Such a polymer is preferably a copolymer of a monomer having no ester bond, such as styrene or vinyltoluene, in addition to a monomer having a ring structure and a monomer having an acid group. Among them, in particular, after solving the above problems, it has been found that the use of vinyl toluene is excellent in an unexpected effect in the art. In other words, by using vinyl toluene, it is possible to form a cured coating film which is improved in the rate of dissolution of an organic solvent or an alkali, and which is easy to prepare a resin composition, and which is excellent in alkali developability as a photosensitive resin.

Hereinafter, the above polymer will be described.

The N-substituted maleimide may be an alkyl-substituted maleate such as N-methylmaleimide, N-isopropylmaleimide or N-cyclohexylmaleimide. An aromatic group-containing maleimide such as an imine, N-phenylmaleimide or N-benzylmaleimide. Among these, N-phenylmaleimide, N-cyclohexylmaleimide, N- are preferable from the viewpoints of solubility in a solvent, thermal decomposition resistance, and industrial availability. Benzyl maleimide. Among these, N-benzylmaleimide is most preferable from the viewpoint of solubility in a solvent and a small color upon heating.

In the above formula (1), the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ¹ and R ² in the above-mentioned ether dimer is not particularly limited, and examples thereof include a methyl group and an ethyl group. a straight or branched alkyl group such as n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, third amyl, stearyl, lauryl or 2-ethylhexyl An aryl group such as phenyl; cyclohexyl, tert-butylcyclohexyl, dicyclopentadienyl, tricyclodecenyl, isobornyl, adamantyl, 2-methyl-2 An alicyclic group such as an adamantyl group; an alkyl group substituted with an alkoxy group such as a 1-methoxyethyl group or a 1-ethoxyethyl group; an alkyl group substituted with an aryl group such as a benzyl group; The carbon number in these is preferably 8 or less. Further, from the viewpoint of heat resistance, it is preferably such as a methyl group, an ethyl group, a cyclohexyl group, a benzyl group or a 2-ethylhexyl group. a substituent of a grade 1 or 2 carbon that is thermally removed. Wherein R ¹ and R ² may be the same substituent or different substituents.

Specific examples of the ether dimer include dimethyl-2,2'-[oxybis(methylene)]bis-2-acrylate (dimethyl-2,2'-[oxybis(methylene)). Bis-2-propenoate], diethyl-2,2'-[oxybis(methylene)]bis-2-acrylate, di(n-propyl)-2,2'-[oxybis(sub. Base]] bis-2-acrylate, di(isopropyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, di(n-butyl)-2,2'- [oxybis(methylene)]bis-2-acrylate, di(isobutyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, di(t-butyl -2,2'-[oxybis(methylene)]bis-2-acrylate, bis(third amyl)-2,2'-[oxybis(methylene)]bis-2-propenoic acid Ester, bis(stearyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, bis(lauryl)-2,2'-[oxybis(methylene) Bis-2-acrylate, bis(2-ethylhexyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, bis(1-methoxyethyl)-2 , 2'-[oxybis(methylene)]bis-2-acrylate, bis(1-ethoxyethyl)-2,2'-[oxybis(methylene)]bis-2-acrylic acid Ester, dibenzyl-2,2'-[oxybis(methylene)]bis-2-acrylate, diphenyl-2,2'- [Oxygen bis(methylene)] bis-2-acrylate, dicyclohexyl-2,2'-[oxybis(methylene)] double -2-acrylate, bis(t-butylcyclohexyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, bis(dicyclopentadienyl)-2,2 '-[Oxobis(methylene)]bis-2-acrylate, bis(tricyclodecenyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, di(( Isodecyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, diamantyl-2,2'-[oxybis(methylene)]bis-2-acrylic acid Ester, bis(2-methyl-2-adamantyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, and the like.

Among these, especially dimethyl-2,2'-[oxybis(methylene)]bis-2-acrylate, diethyl-2,2'-[oxybis(methylene)] double 2-acrylate, dicyclohexyl-2,2'-[oxybis(methylene)]bis-2-acrylate, dibenzyl-2,2'-[oxybis(methylene)] double Preferably, 2-acrylate or bis(2-ethylhexyl)-2,2'-[oxybis(methylene)]bis-2-acrylate is preferred. These ether dimers may be used alone or in combination of two or more.

The ratio of the N-substituted maleimide and/or the ether dimer in the monomer component when the polymer of the present invention is obtained is not particularly limited, but is 2 to 60 mass in the total monomer component, preferably. It is 5~50 mass, more preferably 5~40 mass. When the amount of the N-substituted maleimide and/or the ether dimer is too large, the solubility in a solvent or an alkali may be lowered, or the precipitate may be easily precipitated or gelled during polymerization. On the other hand, if it is too small, there is a lack of heat resistance.

The aforementioned vinyl toluene includes o-vinyltoluene, p-vinyltoluene, and m-vinyltoluene. Among these, it is industrially easy to obtain a mixture of vinyl toluene, p-vinyl toluene, and a mixture of m-vinyl toluene and p-vinyl toluene, especially industrially easy to obtain between vinyl toluene and vinyl. A mixture of toluene is preferred.

The proportion of the vinyl toluene in the monomer component of the polymer is not particularly limited, and is 5 to 80% by mass, preferably 10 to 70% by mass, and more preferably 15 to 60% by mass based on the total monomer component. If the amount of vinyl toluene is too large, the solubility in alkali is lowered. Further, if the amount is too small, the thermal stability is lowered and the decomposition gas is increased during heating.

Examples of the monomer having an acid group (a monomer having an acid group) as long as it has The monomer of the acid group and the polymerizable double bond is not particularly limited, and is preferably acrylic acid or methacrylic acid. In particular, the polymer of the present invention is highly hydrophobic because it contains a vinyl toluene unit as an essential component. Therefore, in order to exhibit sufficient alkali solubility, acrylic acid having a relatively high hydrophilicity is preferred.

The ratio of the monomer having an acid group in the monomer component of the polymer is not particularly limited, and is preferably 5 to 40% by mass, more preferably 8 to 30% by mass, and 8 to 20% by mass based on the total monomer component. %optimal. If the amount of the monomer having an acid group is too small, the alkali solubility may be insufficient. On the other hand, if it is too large, the thermal decomposition resistance is lowered or the solubility in a solvent is lowered. Here, the substantial ratio of the monomer containing an acid group means the ratio which removes the quantity which the reaction of the (meth)acrylic acid glycidyl- In the present invention, as described later, in order to introduce a reactive double bond into a side chain, a reaction such as glycidyl (meth)acrylate may be carried out. At this time, the amount of the acid group-containing monomer to be consumed must be increased to the above amount in advance, and the total amount of the acid group-containing monomer to be added is preferably 15 to 60% by mass, more preferably 20 to 55% by mass, most preferably Good is 20~50% by mass.

The polymer of the present invention may or may not contain a monomer unit other than the above-mentioned necessary monomer unit, and the above-mentioned necessary monomer unit is preferably 50% by mass or more based on the total mass ratio of the polymer. It is more preferably 70% by mass or more, still more preferably 90% by mass or more, and substantially all of the components are the most preferable monomer units.

The arrangement of the monomer units in the polymer of the present invention may be, for example, any of a random copolymer, an alternating copolymer, and a block copolymer.

The polymer of the present invention further preferably contains a polymerizable double bond in the side chain. By the side chain having a polymeric double bond, it can be hardened by heat or light. Therefore, the heat-resistant decomposability is further improved, and the sensitivity to light is improved when the photosensitive resin composition is formed, and the light can be hardened with less light and the mechanical strength after hardening is also increased. The method of introducing a polymerizable double bond into a side chain is preferably a unit of a monomer having a functional group reactive with a double bond and an acid group and the aforementioned polymer acid group. The method of reaction. The monomer having a functional group reactive with a double bond and an acid group is preferably glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, isopropenyloxazoline. Etc., glycidyl methacrylate is the most preferable from the viewpoint of ease of industrial use and reactivity. In the present specification, "(meth)acrylic acid" means both methacrylic acid and acrylic acid.

When the double bond is introduced into the side chain, the double bond equivalent is preferably 400 to 100,000, more preferably 400 to 10,000, and most preferably 500 to 3,000. When the double bond equivalent is too high, the sensitivity to light is lowered, and when the double bond equivalent is too low, the storage stability is deteriorated or the solubility in a solvent is lowered. A method of adding a monomer having a functional group reactive with a double bond and an acid group such as glycidyl (meth)acrylate to the acid group in the polymer can be carried out by a conventional method, and is not particularly limited, and the reaction temperature is relatively high. Preferably, it is 60 ° C to 140 ° C, and an amine compound such as triethylamine or dimethylbenzylamine, an ammonium salt such as tetraethylammonium chloride, a phosphonium salt such as tetraphenylphosphonium bromide or dimethylformamide is used. A known catalyst such as a guanamine compound is preferred.

The above polymers are as described above, and it is preferred that substantially all of the components are essential monomer units, but other copolymerizable monomers may optionally be included.

Examples of the other copolymerizable monomer include aromatic vinyl compounds such as styrene; methyl (meth)acrylate, ethyl (meth)acrylate, and n-propyl (meth)acrylate; Isopropyl acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (methyl) (cyclo) hexyl acrylate, benzyl (meth) acrylate, (meth) acrylate such as 2-hydroxyethyl (meth) acrylate; butadiene or substituted butadiene such as butadiene or isoprene a compound; an ethylene or substituted ethylene compound such as ethylene, propylene, vinyl chloride or acrylonitrile; a vinyl ester such as vinyl acetate; and the like. Among these, methyl (meth)acrylate, cyclohexyl (meth)acrylate, and benzyl (meth)acrylate are preferable. These other monomers which can be copolymerized may be used alone or in combination of two or more. among them, In the present specification, "(meth)acrylic acid" means both methacrylic acid and acrylic acid.

When the monomer component in the case where the polymer is obtained contains the other monomer which can be copolymerized, the content ratio thereof is not particularly limited, but is preferably 50% by mass or less, more preferably 30% by mass or less, more preferably 30% by mass or less. More preferably, it is 10% by mass or less. In particular, since (meth) acrylates are inferior in heat stability, the alcohol is apt to be detached from the ester structure upon heating. Therefore, in the case of (meth) acrylate, it is preferably 20% by mass or less, more preferably 10% by mass or less, and still more preferably substantially no (meth) acrylate. Among them, a unit such as glycidyl (meth)acrylate is added to the unit of (meth)acrylic acid because it is crosslinked during heating, so that the thermal stability is less reduced. In the present invention, the (meth) acrylate is not contained in units of (meth)acrylic acid unit-added glycidyl (meth)acrylate.

The polymerization reaction method of the monomer component is not particularly limited, and various conventional polymerization methods can be employed, but it is particularly preferable to carry out the solution polymerization method. In addition, the polymerization temperature and the polymerization concentration (polymerization concentration (%) = [total weight of monomer components / (total weight of monomer components + solvent weight)] × 100) are due to the type or ratio of the monomer components used, The molecular weight of the target polymer varies, but the polymerization temperature is 40 to 150 ° C, and the polymerization concentration is preferably 20 to 50%, and the polymerization temperature is preferably 60 to 130 ° C, and the polymerization concentration is preferably 30 to 45%.

When a solvent is used for the polymerization of the monomer component, a solvent used in a general radical polymerization reaction may be used as a solvent. Specific examples thereof include ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, and diethylene glycol dimethyl ether; and ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, etc.; methanol, ethanol, isopropanol, n-butanol, ethylene glycol monomethyl ether An alcohol such as propylene glycol monomethyl ether; an aromatic hydrocarbon such as toluene, xylene or ethylbenzene; chloroform; dimethyl hydrazine; These solvents may be used alone or in combination of two or more. Further, especially in the case where the content of the monomer having an acid group exceeds 30% by mass, in order to prevent The precipitation of the weight-retaining body is preferably a mixed solvent of an ester solvent such as propylene glycol monomethyl ether acetate or an alcohol solvent such as propylene glycol monomethyl ether or isopropyl alcohol. Here, the content of the acid group-containing monomer herein means an amount which is increased in order to introduce a reactive double bond to the side chain.

When the monomer component is polymerized, a polymerization initiator which is generally used may be added as needed. The polymerization initiator is not particularly limited, and examples thereof include cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-tert-butyl peroxide, laurel peroxide, and peroxidation. Organic peroxides such as benzamidine, tributyl isopropyl carbonate, third ester of peroxy 2-ethylhexanoate, and tert-butyl peroxy-2-ethylhexanoate; 2'-azobis(isobutyronitrile), 1,1'-azobis(cyclohexanecarbonitrile), 2,2'-azobis (2,4 An azo compound such as dimethylacetonitrile or dimethyl 2,2'-azobis(2-methylpropionate). These polymerization initiators may be used alone or in combination of two or more. In addition, the amount of the initiator to be used may be appropriately set depending on the combination of the monomers to be used, the reaction conditions, the molecular weight of the target polymer, and the like, and is not particularly limited, but a weight average molecular weight which is not gelled can be obtained. From the viewpoint of thousands to tens of thousands of polymers, it is 0.1 to 15% by mass, preferably 0.5 to 10% by mass based on the total monomer component.

When the monomer component is polymerized, a chain transfer agent which is generally used may be added as needed in order to adjust the molecular weight. The chain transfer agent may, for example, be a thiol chain transfer agent such as n-dodecyl mercaptan, mercaptopropionic acid, mercaptoacetic acid or methyl thioglycolate, or an α-methylstyrene dimer. For example, n-dodecyl mercaptan or mercaptopropionic acid is preferred because it has a high chain transfer effect and can reduce residual monomers. In the case of using a chain transfer agent, the amount of the monomer to be used may be appropriately set depending on the combination of the monomers to be used, the reaction conditions, the molecular weight of the target polymer, and the like, and is not particularly limited, but the gelation is not obtained and the weight average is obtained. From the viewpoint of a polymer having a molecular weight of several thousands to several tens of thousands, it is preferably from 0.1 to 15% by mass, more preferably from 0.5 to 10% by mass, based on the total monomer component.

The weight average molecular weight of the polymer of the present invention is not particularly limited, but is preferably from 2,000 to 200,000, more preferably from 5,000 to 100,000. When the weight average molecular weight exceeds 200,000, the viscosity is too high and it is difficult to form a coating film. On the other hand, if it is less than 2,000, it tends to be difficult to exhibit sufficient heat resistance. Among them, the method for measuring the weight average molecular weight is shown in the following examples.

The polymer preferably has an acid value of 30 to 300 mgKOH/g, more preferably 50 to 200 mgKOH. When the acid value is less than 30 mgKOH/g, it is difficult to apply to alkali development. When it exceeds 300 mgKOH/g, the viscosity tends to be too high, and it tends to be difficult to form a coating film. Further, the solubility in the solvent is lowered, and precipitation occurs during the synthesis, and there is a possibility that the solvent cannot be stirred.

The polymer of the present invention is particularly suitable as a binder polymer which is a thermosetting resin composition or a photosensitive resin composition, but is particularly preferable as a binder of a photosensitive resin composition. When a binder is used as the photosensitive resin composition, in addition to the above-mentioned polymer, a radical polymerizable compound, a photopolymerization initiator, and a solvent may be blended, if necessary, a sensitizer, a pigment, a pigment dispersant, and an interfacial activity. Agents and the like are preferred.

Examples of the photopolymerization initiator include thioxanthones such as 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; and diphenyl groups such as diphenyl ketone. Ketones; 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-propan-1-one, 2-benzyl-2-dimethylamino-1-( 4-morpholinylphenyl)-butanone-1; acylphosphine oxides and xanthones, and the like may be used alone or in combination of two or more.

Further, the content thereof is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass based on the above polymer.

The polymer of the present invention may contain a solvent as a diluent as needed. The solvent is not particularly limited as long as it dissolves the polymer uniformly and does not react. Specific examples thereof include tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, and diethylene glycol dimethyl ether. Ethers; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexane; ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, etc. ; alcohols such as methanol, ethanol, isopropanol, n-butanol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether; aromatic hydrocarbons such as toluene, xylene, ethylbenzene; chloroform, dimethyl Oh; wait. Among them, the content of the solvent can be appropriately set depending on the optimum viscosity at the time of use.

The polymer of the present invention has high heat resistance and a small amount of decomposition gas during heating, and can form an extremely excellent coating film, and has a fast dissolution rate with respect to an organic solvent or an alkali, and thus can be suitably used, for example, as a photosensitive resin composition. , various coating agents, coatings and other uses.

Hereinafter, the present invention will be described in detail by way of examples, but the scope of the invention is not limited to the examples. Unless otherwise specified, "parts" means "parts by weight". In the following examples, various physical properties and the like were measured in the following manner.

<weight average molecular weight>

The weight average molecular weight was measured by using HLC-8220GPC (manufactured by Tosoh Corporation) using polystyrene as a standard material and THF (tetrahydrofuran) as a solution.

<acid price>

Accurately weigh 3g of resin solution, dissolve it in 70g/water 30g mixed solvent, use thymol blue as indicator, titrate with 0.1N KOH aqueous solution, and determine the solid content per 1g from the concentration of solid component. Acid price.

Example

Example 1

To a separable flask equipped with a cooling tube as a reaction vessel, 100 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) was added, and after nitrogen substitution, the temperature was raised to 90 °C. On the other hand, in the dropping tank 1, 20.0 parts of dimethyl-2,2'-[oxybis(methylenebis)]-2-acrylate, 25.0 parts of acrylic acid, and peroxy-2-ethylhexanoic acid were added. 2.0 parts of tributyl ester and 80 parts of PGMEA were mixed. Again, in the drop tank 2 55 parts of vinyl toluene (mixture of m-vinyltoluene and p-vinyltoluene of 60 to 40) and 2.0 parts of n-dodecylmercaptan were mixed. While maintaining the reaction temperature at 90 ° C, the mixture was dropped from the dropping tanks 1 and 2 at a constant rate to the reaction vessel at 4.0 hours. After completion of the dropwise addition, the mixture was kept at 90 ° C for 30 minutes, and then 0.5 part of perbutyl 2-ethylhexanoate was added, and the reaction was further continued at 90 ° C for 30 minutes. Thereafter, the reaction temperature was raised to 115 ° C, and the reaction was continued for 1.5 hours. Once cooled to room temperature, 19.7 parts of glycidyl methacrylate, 0.10 parts of 6-t-butyl-2,4-xylenol, 0.30 parts of triethylamine, and a nitrogen concentration of 7% were added. The air mixed gas was bubbled while raising the temperature to 110 ° C, and the reaction was carried out for 2 hours. Thereafter, the temperature was raised to 115 ° C and allowed to react for 5 hours, and the reaction was completed, followed by cooling to room temperature to obtain a polymer solution 1.

The physical properties of the obtained polymer solution 1 were measured, and the weight average molecular weight measured by GPC (gel permeation chromatography) of the standard substance was polystyrene was 16,000, and the solid content concentration obtained by drying at 160 ° C under vacuum was 38.1. %, the acid value per unit solid content determined by the titration method was 100 mgKOH/g.

100 parts by weight of the polymer solution, 30 parts by weight of dipentaerythritol pentaacrylate, 3 parts by weight of Iruga Gaya 907 (manufactured by Ciba-geigy Co., Ltd.), and 500 parts by weight of PGMEA After mixing, it was spin-coated on a glass substrate, and dried at 90 ° C for 3 minutes to form a coating film 1 having a film thickness of 3 μm.

The coating film 1 was immersed in PGMEA at 20 ° C to visually observe the time until the film was completely dissolved, and the time until the film was dissolved was 15 seconds. The coating film 1 was subjected to UV exposure at 300 mJ/cm ² with a high pressure mercury lamp, and then heated at 200 ° C for 30 minutes to complete the hardening. The obtained cured film was cut, and the weight reduction rate at 130 ° C for 30 minutes as measured by TG-DTA method (thermo-differential thermal analysis) was 1.1%. The measurement results obtained and the like are shown in Table 1. Table 1 below shows the compositions of the polymer components of Examples 1 to 3 and Comparative Examples 1 to 3, the physical properties of the polymer solution, the coating film, and the cured film.

Example 2

As shown in Table 1, N-benzyl maleimide was substituted for dimethyl-2,2'-[oxybis(methylenebis)]-2-acrylate, and In the same manner as in Example 1, a coating film and a cured film were produced, and physical properties and the like were measured.

The time during which the coating film was dissolved in PGMEA was 14 seconds.

Further, the cured film had a weight reduction rate of 0.6% at 230 ° C for 30 minutes.

Example 3

To a separable flask equipped with a cooling tube as a reaction vessel, 100 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) and 50 parts of propylene glycol monomethyl ether (PGME) were added, and after nitrogen substitution, the temperature was raised to 90 °C. On the other hand, 15.0 parts of N-benzylmaleimide, 37.2 parts of acrylic acid, 2.0 parts of tert-butyl peroxy-2-ethylhexanoate, 56 parts of PGMEA, and 24 parts of PGME were mixed in the dropping tank 1. Further, 47.8 parts of vinyl toluene (mixture of m-vinyltoluene and p-vinyltoluene of 60 to 40) and 3.0 parts of n-dodecylmercaptan were mixed in the dropping tank 2. While maintaining the reaction temperature at 90 ° C, the mixture was dropped from the dropping tanks 1 and 2 at a constant rate to the reaction vessel at 4.0 hours. After completion of the dropwise addition, the mixture was kept at 90 ° C for 30 minutes, and then 0.5 part of perbutyl 2-ethylhexanoate was added, and the reaction was further continued at 90 ° C for 30 minutes. Thereafter, the reaction temperature was raised to 115 ° C, and the reaction was continued for 1.5 hours. After cooling to room temperature, 50.0 parts of glycidyl methacrylate, 0.10 parts of 6-t-butyl-2,4-xylenol, 0.30 parts of triethylamine, and a nitrogen concentration of 7% were adjusted. The air mixture was bubbled while raising the temperature to 110 ° C, and the reaction was carried out for 16 hours. The reaction was terminated in the same manner as in Example 1, and then cooled to room temperature to obtain a polymer solution.

The obtained polymer solution had a weight average molecular weight of 13,000, a solid content concentration of 36.1%, and an acid value per unit solid content of 80 mgKOH/g. The same preparation as in Example 1 was carried out to form a coating film, and the time until the film was dissolved in PGMEA was 16 seconds.

Further, the cured film was reduced in weight by 0.6% at 230 ° C for 30 minutes as measured by the TG-DTA method.

Further, the coating film was exposed to UV light of 50 mJ/cm ² through a UV exposure apparatus (TME-150 RNS manufactured by Topcon Co., Ltd.) through a line having a line width of 15 μm and a line & space mask, and dried at 90 ° C. After a minute, development was carried out for 20 seconds with a 0.01 KOH aqueous solution using a Spiegel developing machine (ADE-3000S manufactured by Actes Co., Ltd.). Fig. 1 is a view showing the state of a glass substrate obtained by alkali-developing a coating film after exposure.

In Fig. 1, the lattice portion (rectangular pattern) located at the upper portion is an exposed portion exposed through the reticle, and the periphery thereof is an unexposed portion protected by the reticle. As shown in Fig. 1, a complete pattern was formed in the exposed portion due to curing of the coating film, and the coating film was dissolved in the unexposed portion, and it was confirmed that the remaining residue was not dissolved.

Further, even if the development time in the same step as described above was carried out for 30 seconds, there was no pattern defect.

Comparative example 1

The same operation as in Example 1 was carried out, except that benzyl methacrylate was used in place of vinyltoluene as shown in Table 1. The dissolution time of the coating film was 10 seconds, and the weight reduction rate at 230 ° C for 30 minutes was 3.5%.

Comparative example 2

The same operation as in Example 1 was carried out, except that styrene was used instead of vinyltoluene as shown in Table 1. The dissolution time of the coating film was 24 seconds, which was slower than that of Example 1. Further, the weight reduction rate at 230 ° C for 30 minutes was 1.4%.

Comparative example 3

The same operation as in Example 3 was carried out, except that styrene was used instead of vinyltoluene as shown in Table 1. The dissolution time of the coating film dissolved into PGMEA was 30 seconds, compared with Example 3. long.

The weight reduction rate of the cured film at 230 ° C for 30 minutes was 1.1%.

Alkali development was carried out under the same conditions as in Example 3. Fig. 2 is a view showing a state of a glass substrate obtained by alkali-developing a coating film after exposure, and is formed in the same manner as in Fig. 1 to form an exposed portion and an unexposed portion. As shown in FIG. 2, the exposure portion is formed with a pattern. In the unexposed portion, the coating film was not dissolved, and it was confirmed that the remaining development residue was dissolved.

Further, if the development time was set to 30 seconds in the same procedure as described above, the residue of the unexposed portion disappeared, but defects were observed in a part of the pattern. From the above, it is known that the allowable range of development time, that is, the development limit of styrene and vinyl toluene is very narrow, and the alkali developability is poor.

As is apparent from the above examples and comparative examples, the polymer of the present invention has a small weight reduction rate and is excellent in thermal decomposition resistance, and is also excellent in solvent solubility and alkali developability.

The technical essence of the polymer of the present invention is that vinyltoluene is used in addition to the monomer having a ring structure and the monomer having an acid group in the monomer component formed.

One of the features of the present invention is that the N-substituted maleimide monomer and/or the ether dimer monomer represented by the above formula (1) form a ring structure and exhibits polymerization by such a structure. The heat resistance of the object. It is clear from the above chemical structures that one of the above-mentioned monomer groups of the single system used in the above examples is only referred to as an N-substituted maleimide monomer and/or an ether dimer monomer. The monomer of the category can exhibit the effects of the present invention.

Further, in the case where the monomer component of the polymer is formed, since the above-described three components are used, the structure can be substantially free of ester bonds, and therefore heat resistance is improved. The essence of the present invention is that vinyltoluene is used in a monomer having no ester bond such as styrene or vinyl toluene, which can be exemplified by the above examples and comparative examples.

Further, in the above embodiment, it has been confirmed that the ratio of the above three components can achieve an advantageous effect if it is within the preferred range described in the present specification.

(industrial use)

The polymer of the present invention is a binder polymer, a thermosetting resin, and various coating materials used as a photosensitive resin composition such as a liquid crystal display or a printed wiring board.

The present application claims priority based on Japanese Patent Application No. 2007-186577, "New Polymer", filed on Jan. 18, 2007. The contents of this application are hereby incorporated by reference in its entirety.

Claims (5)

A polymer characterized by (a) 2 to 60% by mass of an N-substituted maleimide monomer substituted with an alkyl group or an aromatic group in the total monomer component, and (b) total 5 to 80% by mass of vinyl toluene in the monomer component, and (c) 5 to 40% by mass of (meth)acrylic acid as a necessary component in the total monomer component, total monomer component The content ratio of the (meth) acrylate in the polymer is 20% by mass or less based on the polymer. The polymer of claim 1, further comprising a polymerizable double bond in the side chain. The polymer of claim 1 or 2, wherein the N-substituted maleimide monosystem is selected from the group consisting of N-phenylmaleimide, N-cyclohexylmaleimide, and N- At least one of the group consisting of benzyl maleimide. A polymer according to claim 1 or 2, wherein (c) (meth)acrylic acrylic acid. For example, the polymer of the second application of the patent scope has a double bond equivalent of 500 to 3,000.