JP2008019293A - Polyester containing terpene phenol unit - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new polyester used as a photosensitive resin having flexibility. <P>SOLUTION: The polyester has a terpene skeleton represented by general formula (1) (wherein, X represents a terpene diphenoxy group; Y represents a residue after removing carboxy groups from a tetrabasic acid dianhydride; R represents an H or a CH<SB>3</SB>; R' represents an H or a residue of a carboxy group-blocking agent; and n represents an integer of 1-40). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a polyester containing a terpene phenol unit in the skeleton, and more particularly to a novel polyester that can be used as a photosensitive resin capable of alkali development as an example.

  Conventionally, a photosensitive resin has been used as a permanent protective mask such as a resist material or a solder resist in a printed wiring board. The photosensitive resin is cured by light irradiation in the presence of a suitable photopolymerization initiator. For example, Patent Document 1 below proposes an epoxy acrylate compound having a cardophenol resin skeleton.

In addition, regarding such a photosensitive resin, the following Patent Document 2 discloses an alkali-soluble photosensitive resin that is soluble in an alkaline aqueous solution in an uncured state and becomes insoluble after curing, thereby enabling alkali development. A compound obtained by subjecting the epoxy acrylate compound of Patent Document 1 to an addition reaction of a carboxylic acid anhydride has been proposed.
JP 7-48424 A JP-A-5-70528

  The above-mentioned conventional compound is an epoxy acrylate resin in which the cardophenol contained in the skeleton has a rigid structure, and both ends are simply added with acrylic acid or methacrylic acid at the ends of an epoxy resin that is glycidyl etherified. There is a disadvantage that it is inferior in flexibility.

  An object of the present invention is to provide a novel polyester used as a flexible photosensitive resin.

The polyester according to the first aspect of the present invention is represented by the following general formula (1).

In the formula, X is a terpene diphenoxy group represented by the following formula (2) or (3), and one molecule may contain a mixture of the formula (2) and the formula (3). Y is a residue excluding a carboxyl group of an organic compound having four carboxyl groups, R is H or CH ₃ , R ′ is a residue of H or a carboxyl group blocking agent, and n is an integer of 1 to 40 Indicates.

In addition, the polyester according to the second invention of the present invention includes at least one of an epoxy (meth) acrylate represented by the following general formula (4) and an epoxy (meth) acrylate represented by the following general formula (5); A polyester having a weight average molecular weight of 3,000 to 100,000 obtained by condensation polymerization with a tetrabasic acid dianhydride represented by the following general formula (6).

In the formula, R represents H or CH ₃ .

  In formula, Y shows the residue except the carboxyl group of the organic compound which has four carboxyl groups.

  According to the present invention, together with the flexibility of the terpene phenol unit contained in the skeleton, the terpene phenol unit is a polyester linked via an ester bond with a tetrabasic acid dianhydride, A photosensitive resin having flexibility (flexibility) is obtained.

  The polyester according to the present invention comprises a terpene diphenol diglycidyl ether di (meth) acrylate represented by the general formula (4) and / or (5) and a tetrabasic acid diacid represented by the general formula (6). It can be produced by an esterification reaction (an condensation polymerization reaction) with an anhydride.

The di (meth) acrylate can be synthesized by synthesizing terpene diphenol, that is, terpene phenol resin by diglycidyl ether to synthesize an epoxy resin, and adding acrylic acid or methacrylic acid to both ends of the epoxy resin. . In formulas (4) and (5), the case of R = H is diacrylate, and the case of R = CH ₃ is dimethacrylate, and both are collectively referred to as di (meth) acrylate. The epoxy acrylate resin thus obtained preferably has an acid value of less than 10 mg KOH / g and an epoxy equivalent of 10,000 to 20,000.

  Here, the acid value was measured by weighing 1 g of a sample in an Erlenmeyer flask, dissolving in 50 ml of dioxane, titrating with 0.1 M KOH aqueous solution using phenolphthalein as an indicator, and changing the color from colorless to pink. Desired. The epoxy equivalent is a predetermined amount (˜5 g) of a sample weighed in a beaker, dissolved in 50 ml of chloroform, added with 5 ml of a 20% acetic acid solution of tetraethylammonium bromide, and 0.1 N perchlorine with crystal violet as an indicator. Titration with an acid-acetic acid solution is performed by measuring the point at which the color changed from purple to blue-violet.

The terpene diphenol is represented by the following formula (7) or formula (8), and is represented by the 1,3-terpene phenol resin represented by formula (7) and 2 represented by formula (8). , 8-terpene phenol resin can be used alone, or a mixture of both can be used. Usually, a mixture of the two is used, and the mixing ratio is preferably a weight ratio of formula (7): formula (8) = 80-60: 20-40.

As a method for synthesizing the epoxy resin, synthesis of a general epoxy resin can be applied. For example, the epoxy resin can be synthesized by reacting the terpene diphenol with epichlorohydrin in the presence of a basic catalyst. Thus, terpene diphenol diglycidyl ether represented by the following formula (9) or formula (10) is obtained. The epoxy resin thus obtained preferably has an epoxy equivalent of 260 to 300.

Examples of the tetrabasic dianhydride include, but are not limited to, seven aromatic tetrabasic dianhydrides exemplified below. Particularly preferred are those represented by the following formulas (11), (12) and (13).

  The method of the esterification reaction is not particularly limited. For example, the above-mentioned general can be obtained by dissolving the di (meth) acrylate with heating in an organic solvent, adding a tetrabasic acid dianhydride, and reacting with stirring. The polyester of the present invention, which is a condensation polymerization resin of an epoxy (meth) acrylate represented by the formula (1) and a tetrabasic acid dianhydride, can be synthesized.

  The weight average molecular weight of the polyester thus obtained can be adjusted by changing the solvent amount and the reactive group mass in the esterification reaction. In the present invention, the weight average molecular weight is 3,000 to 100,000. It is preferable that it is 5,000 to 25,000. Moreover, although it is related also with a weight average molecular weight, in said formula (1), it is preferable that n is 1-40. When the weight average molecular weight is smaller than the above range, sufficient flexibility and adhesion cannot be obtained. On the other hand, when the weight average molecular weight is too large, photocurability and alkali solubility in an uncured state become poor. Here, the weight average molecular weight is a polystyrene equivalent weight average molecular weight measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran). The polyester preferably has an acid value of 60 to 70 mgKOH / g for good alkali solubility in an uncured state.

  In the polyester obtained by the esterification reaction, in formula (1), R ′ is all H, that is, each tetrabasic acid dianhydride has 2 or 3 carboxyl groups in the residue. Thus, it has excellent solubility in an aqueous alkali solution. In order to adjust the alkali solubility, the carboxyl group may be blocked with a blocking agent. It is possible to control the acid value of the present polyester by changing the blocking amount of the carboxyl group, and although not particularly limited, the acid value is preferably 20 to 80 mgKOH / g, more preferably 30 to 70 mgKOH. / G. In addition, although it is good also in the kind of tetrabasic acid dianhydride, it is preferable that R 'is 50 mol% or more in order to ensure alkali developability, More preferably, 70 mol% or more is H. .

  Such a carboxyl group blocking agent is not particularly limited as long as it has a functional group capable of reacting with a terminal carboxyl group, and examples thereof include various known terminal blocking agents such as glycidyl ether and carbodiimide. Preferred are glycidyl ethers such as phenyl glycidyl ether, butylphenyl glycidyl ether, and resorcing ricidyl ether. In this case, the epoxy equivalent of the blocked polyester is preferably 60,000 or more.

  Since the polyester comprising the above has a photopolymerizable acrylic acid or methacrylic acid moiety, it can be photopolymerized in the presence of a suitable photopolymerization initiator, and can be cross-linked and cured by photopolymerization to produce an alkaline aqueous solution. It becomes difficult to dissolve. On the other hand, since it dissolves in an aqueous alkali solution in an uncured state, the film is partially irradiated with light to exhibit alkali developability that leaves a cured portion and dissolves and removes the uncured portion with an aqueous alkali solution. In addition, this polyester has good adhesion to various base materials, small curing shrinkage, excellent heat resistance (high Tg), and can form a hard film. Furthermore, since the terpene phenol unit contained in the skeleton has a relatively flexible structure and the terpene phenol unit is a polyester linked via an ester bond with a tetrabasic acid dianhydride, It has flexibility.

  This polyester may be polymerized by itself, or may be used in combination with various photopolymerizable monomers, as a coating agent for glass and various films, and a paint applied to glass and various films. Furthermore, it can be suitably used as a binder for resist materials such as printed wiring board resists and color resists.

  Hereinafter, although an example is given and an embodiment of the present invention is explained still more concretely, the present invention is not limited to the following example.

(Synthesis Example 1: Terpene diphenol diglycidyl ether)
To a 5 L four-necked flask equipped with a condenser and a stirrer, terpene diphenol (1,3-terpene phenol resin: 2,8-terpene phenol resin = 70: 30 (weight ratio), “YP-90 manufactured by Yashara Chemical Co., Ltd.” “) 1070 g, epichlorohydrin 1520 g and DMSO 1700 g were charged and stirring was started. After heating to 50 ° C. and dissolution, 290 g of caustic soda was added, and a reaction was performed by heating at 65 ° C. to 90 ° C. for 10 hours. The progress and end point of the reaction were carried out by measuring the epoxy equivalent, and after the epoxy equivalent reached the purpose, DMSO was distilled off under reduced pressure at 90-100 ° C. Thereafter, redissolved in toluene at 50 to 70 ° C., further added with distilled water, washed with water, left to stand and separated, and the organic layer was desolvated under reduced pressure. 1260 g of a resin mixture was obtained. The epoxy equivalent of the obtained epoxy resin was 260.

In the nuclear magnetic resonance spectrum (1H-NMR: in CDCl ₃ solvent, tetramethylsilane standard, ppm) of this product, as shown in FIG. 1, a peak derived from the benzene ring of the terpene skeleton (8H ), Δ3.3, δ3.9 to 4.2, peaks derived from the epoxy moiety (6H), and δ0.7 to 0.9, peaks derived from the two methyl groups of the isopropyl group emerging from the terpene skeleton (6H). ) Was recognized.

Further, in the infrared absorption spectrum of the (IR), as shown in FIG. 2, an aromatic ether 1241Cm ^-1, absorption based on epoxy ring, absorption based on aromatic ether 1036,828Cm ^-1 was observed.

  From the above results, it was confirmed that this was a mixture of terpene diphenol diglycidyl ethers represented by formula (9) and formula (10).

(Synthesis Example 2: Terpene diphenol diglycidyl dimethacrylate)
A 5 L four-necked flask equipped with a condenser and a stirrer was charged with 1000 g of the epoxy resin mixture obtained in Synthesis Example 1, 1.0 g of hydroquinone monomethyl ether and 350 g of methacrylic acid, and stirring was started. After dissolving at 60 ° C., 8 g of tetraethylammonium bromide was added, and the heating reaction was continued at 70 to 90 ° C. until the acid value was 8 mg KOH / g and the epoxy equivalent was 17000. After 15 hours, the end point was confirmed by the acid value and the epoxy equivalent, followed by cooling to obtain 1300 g of a mixture of epoxy methacrylate resins represented by the following formula (14) and formula (15). The epoxy equivalent of the obtained epoxy methacrylate resin was 17000, the acid value was 8 mgKOH / g, and the hydroxyl value was 165 mgKOH / g.

In the 1H-NMR spectrum (CDCl ₃ solvent, based on tetramethylsilane, ppm) of this product, as shown in FIG. 3, peaks (4H) derived from methacrylic acid double bonds at δ5.6 and δ6.1, A peak (10H) in which the peaks of δ3.3 and δ3.9 to 4.2 in the above formulas (9) and (10) were shifted by the ring opening of epoxy was observed at δ3.9 to 4.4. .

Further, in the IR spectrum of this product, absorption based on an ester bond was observed at 1720 cm ^{−1 as} shown in FIG.

  From the above results, it was confirmed that this was a mixture of terpene diphenol diglycidyl dimethacrylate represented by the formulas (14) and (15).

(Synthesis Example 3: Terpene diphenol diglycidyl diacrylate)
In place of methacrylic acid in Synthesis Example 2, 293 g of acrylic acid was charged, and the others were reacted in the same manner to obtain 1200 g of an epoxy acrylate resin mixture represented by the following formulas (16) and (17). The epoxy equivalent of the obtained epoxy acrylate resin was 16500, the acid value was 6 mgKOH / g, and the hydroxyl value was 171 mgKOH / g.

(Synthesis Example 4: Methacryloyl group-containing polyester having a terpene skeleton)
A 5 L four-necked flask equipped with a condenser and a stirrer was charged with 670 g of the epoxy methacrylate resin mixture obtained in Synthesis Example 2 and 1300 g of methyl isobutyl ketone, and stirring was started. After heating and dissolving at 60 ° C., 220 g of pyromellitic anhydride (manufactured by Daicel Chemical Industries, Ltd.) represented by the above formula (11) is added, and a stirring reaction is performed at 80 ° C. The acid value is 67.9 mgKOH / g, The reaction was continued until the variation of the acid value was 2 mgKOH / g or less. After completion of the reaction, distilled water is added to the reaction solution, followed by washing with water and standing separation. The organic layer is recovered, and the solvent is distilled off at 50 to 70 ° C. under reduced pressure, and then represented by the following formula (18). 860 g of a polyester resin (where X is a terpene diphenoxy group represented by the above formula (2) or (3), R is CH ₃ , R ′ is H, and n is 20) was obtained.

The weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of this resin was 18000. The acid value was 61.2 mgKOH / g.

In the 1H-NMR spectrum (CDCl ₃ solvent, based on tetramethylsilane, ppm) of this product, as shown in FIG. 5, peaks derived from the benzene ring of the terpene skeleton and the benzene ring of pyromellitic acid at δ 6.9 to 7.6. , Δ5.8 and δ6.2 are peaks derived from the double bond portion of methacrylic acid, δ1.1 to 2.2 are peaks derived from the cyclohexane skeleton of terpene diphenol, and δ0.7 to 0.9 are emitted from the terpene skeleton. Peaks derived from the two methyl groups of the isopropyl group were observed.

Also, in the IR spectrum of the as shown in FIG. 6, the absorption based on an ester bond to 1735 cm ^-1, absorption based on aromatic ester 1735,1241,1102Cm ^-1 was observed.

  From the above results, it was confirmed that this was a methacryloyl group-containing polyester having a terpene skeleton represented by the formula (18).

(Synthesis Example 5: acryloyl group-containing polyester having a terpene skeleton)
In place of the epoxy methacrylate resin used in Synthesis Example 4, 660 g of a mixture of the epoxy acrylate resin obtained in Synthesis Example 3 was charged, and the others were reacted in the same manner as in Synthesis Example 4 and represented by the above formula (18). 840 g of a polyester resin (where X is a terpene diphenoxy group represented by the above formula (2) or (3), R is H, R ′ is H, and n is 17) was obtained.

  It was the polystyrene conversion weight average molecular weight 15000 measured by the gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of this resin. The acid value was 60.9 mgKOH / g.

(Synthesis Example 6: carboxyl group cap of methacryloyl group-containing polyester having a terpene skeleton)
A 1 L four-necked flask equipped with a condenser and a stirrer was charged with 275 g of the polyester resin obtained in Synthesis Example 4 and 275 g of propylene glycol monomethyl acetate, and the stirring was started. 0.5 g was added, 30 g of phenylglycidyl ether (trade name: Epiol P (manufactured by NOF Corporation)) was added as a carboxyl group blocking agent, and the mixture was heated and stirred at 80 to 90 ° C. The reaction is continued until the fluctuation of the acid value becomes 2 mgKOH / g or less, and after the acid value reaches the target, it is cooled to room temperature, and the polyester resin represented by the above formula (18) (where X is the above formula ( 2) or a terpene diphenoxy group represented by (3), R is CH ₃ , R ′ is H or C ₆ H ₅ OCH ₂ CH (OH) CH ₂ (wherein H is 78% and a blocking agent residue) Is 22%) and n is 20.

  The polystyrene-reduced weight average molecular weight of this resin measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) was 21,000. The acid value was 52.1 mgKOH / g.

In the 1H-NMR spectrum (CDCl ₃ solvent, based on tetramethylsilane, ppm) of this product, as shown in FIG. 7, in addition to the polyester resin obtained in Synthesis Example 4, δ 6.9 to 7.6 A peak derived from the benzene ring of phenylglycidyl ether used for blocking the carboxylic acid was observed.

Further, in the IR spectrum of this product, as shown in FIG. 8, absorption based on an aromatic ether was observed at 1047 cm ⁻¹ . That is, the absorption of 1047 cm ⁻¹ was larger than that of the polyester resin obtained in Synthesis Example 4 by the introduction of phenylglycidyl ether.

(Synthesis Example 7: carboxyl group cap of acryloyl group-containing polyester having a terpene skeleton)
In place of the polyester resin obtained in Synthesis Example 4, 300 g of the polyester resin obtained in Synthesis Example 5 was charged, and the others were reacted in the same manner as in Synthesis Example 6 to obtain a polyester resin represented by the following formula (18) ( However, X is a terpene diphenoxy group represented by the above formula (2) or (3), R is H, R ′ is H or C ₆ H ₅ OCH ₂ CH (OH) CH ₂ (where H is 80% And 340 g of a sequestering residue of 20%) and n of 17.

  The weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of this resin was 25000. The acid value was 50.0 mgKOH / g.

(Synthesis Example 8: methacryloyl group-containing polyester having a terpene skeleton)
Into a 5 L four-necked flask equipped with a condenser and a stirrer, 670 g of the epoxy methacrylate resin mixture obtained in Synthesis Example 2 and 1470 g of methyl isobutyl ketone were charged, and stirring was started. After heating and dissolving at 60 ° C., 313 g of oxydiphthalic dianhydride (manac Co., Ltd.) represented by the above formula (12) was added, and the mixture was stirred at 80 ° C., and the acid value was 53.3 mgKOH / g. The reaction was continued until After completion of the reaction, distilled water is added to the reaction solution, followed by washing with water and standing separation. The organic layer is recovered, and the solvent is distilled off at 50 to 70 ° C. under reduced pressure, and then represented by the following formula (19). 800 g of a polyester resin (where X is a terpene diphenoxy group represented by the above formula (2) or (3), R is CH ₃ , R ′ is H, and n is 8) was obtained.

The weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of this resin was 9000.

(Synthesis Example 9: methacryloyl group-containing polyester having a terpene skeleton)
Into a 5 L four-necked flask equipped with a condenser and a stirrer, 670 g of the epoxy methacrylate resin mixture obtained in Synthesis Example 2 and 1660 g of methyl isobutyl ketone were charged, and stirring was started. After heating and dissolving at 60 ° C., 434 g of ethylene glycol bisanhydro trimellitate represented by the above formula (13) (manufactured by New Japan Science Co., Ltd.) is added and stirred at 80 ° C., and the acid value is The reaction was continued until 46.2 mg KOH / g. After completion of the reaction, distilled water is added to the reaction solution, and after washing and standing separation, the organic layer is recovered, the solvent is distilled off at 50 to 70 ° C. under reduced pressure, and then represented by the following formula (20). 900 g of a polyester resin (where X is a terpene diphenoxy group represented by the above formula (2) or (3), R is CH ₃ , R ′ is H, and n is 12) was obtained.

The weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of this resin was 13,000.

(Example)
For each resin of Synthesis Examples 3 to 9, 100 parts by weight of propylene glycol monomethyl acetate as a solvent and 3 parts by weight of a photopolymerization initiator (“Irgacure 184” manufactured by Ciba Geigy) are added to 100 parts by weight of the resin. After drying) = 100 μm was applied on the substrate. Then, after drying under reduced pressure at 120 ° C. for 5 hours, UV irradiation was performed so that the integrated illuminance was 2000 mj with a single high pressure mercury lamp of 80 W / cm at a focal length of 8 cm. About the obtained cured film, alkali solubility, adhesiveness with a base material, cure shrinkage rate, heat resistance, pencil hardness, and flexibility were evaluated. Each evaluation method is as follows.

-Alkali solubility: The film before hardening and the film after hardening were immersed in 2.5% NaOH aqueous solution, and solubility was evaluated.

-Adhesion with the base material: Cut through the film on the base material (glass plate), make cuts that reach the ground surface in a grid pattern, apply adhesive tape on the grid pattern, and remain after peeling (The remaining number x for 100 grids is displayed as “x / 100”).

-Curing shrinkage ratio: specific gravity was measured based on JIS K0061-1992 for the test samples before and after curing, and the volume shrinkage ratio was calculated by the following formula.

Volume shrinkage (%) = {(specific gravity after curing−specific gravity before curing) / specific gravity after curing} × 100
-Heat resistance: “Rheogel E-4000” manufactured by UBM was used, and the glass transition point (Tg) giving the maximum value of tanσ was determined by the dynamic viscoelasticity measurement method as tanσ = loss elastic modulus / dynamic elastic modulus. .

Pencil hardness: Based on JIS K5600-5-4, the resistance of the film to scratches or other defects generated as a result of pressing a pencil having a prescribed size and hardness on the film was evaluated.

・ Flexibility: For a test sample prepared using a tin plate (150 × 50 × 0.3 mm) as a base material, insert it with a bending tester so that the coating surface is outside the mandrel, and quickly It was bent about 180 degrees around the mandrel. Thereafter, the test sample was taken out and examined for cracking and peeling by visual observation. For each of the three test samples, when the coating film was not cracked or peeled off, it was determined to be acceptable as being flexible enough to withstand bending. Table 1 shows the minimum diameter that was judged in order from the mandrel with the largest diameter.

  As shown in Table 1, each polyester according to this example has good adhesion to the substrate, small curing shrinkage, excellent heat resistance and a hard film, and the film has excellent flexibility. Met. Further, the uncured portion was soluble in an alkaline aqueous solution and became insoluble by photocuring, so that alkali development was possible.

  The polyester of the present invention is suitable for coating on various substrates such as glass and film, as a raw material for coatings applied to these substrates, and further as a binder for resist materials such as resists for printed wiring boards and color resists. Can be used.

4 is a graph showing the measurement results of 1H-NMR spectrum for the epoxy resin of Synthesis Example 1. It is a graph which shows the measurement result of IR spectrum about the epoxy resin of the synthesis example 1. It is a graph which shows the measurement result of the 1H-NMR spectrum about the epoxy methacrylate resin of the synthesis example 2. It is a graph which shows the measurement result of IR spectrum about the epoxy methacrylate resin of the synthesis example 2. It is a graph which shows the measurement result of the 1H-NMR spectrum about the polyester resin of the synthesis example 4. It is a graph which shows the measurement result of IR spectrum about the polyester resin of the synthesis example 4. It is a graph which shows the measurement result of the 1H-NMR spectrum about the polyester resin of the synthesis example 6. It is a graph which shows the measurement result of IR spectrum about the polyester resin of the synthesis example 6.

Claims (2)

Polyester represented by the following general formula (1).

(In the formula, X is a terpene diphenoxy group represented by the following formula (2) or (3), and one molecule may contain a mixture of formula (2) and formula (3). , Y is a residue excluding a carboxyl group of an organic compound having four carboxyl groups, R is H or CH ₃ , R ′ is a residue of H or a carboxyl group blocking agent, and n is an integer of 1 to 40 Show.)

At least one of an epoxy (meth) acrylate represented by the following general formula (4) and an epoxy (meth) acrylate represented by the following general formula (5), and a tetrabasic acid diacid represented by the following general formula (6) A polyester having a weight average molecular weight of 3,000 to 100,000 obtained by condensation polymerization with an anhydride.

(In the formula, R represents H or CH _3. )

(In the formula, Y represents a residue excluding the carboxyl group of an organic compound having four carboxyl groups.)

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