JP2011153193A - Phosphorus-containing vinyl monomer, process for producing the same, phosphorus-containing polymerized product using the process and resin composition containing the polymerized product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a phosphorus-containing vinyl monomer which takes an environmental aspect by being non-halogenated into consideration, has excellent flame retardance, and can inhibit the exudation and deposition of a flame retardant component and a process for producing the same. <P>SOLUTION: The phosphorus-containing vinyl monomer is obtained by reacting a substituted or nonsubstituted 9,10-dihydro-9-oxa-10-phospha/phenanthrene-10-oxide with an α, β-unsaturated carboxylic acid ester of a terminal-unsaturated alcohol. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  TECHNICAL FIELD The present invention relates to a phosphorus-containing vinyl monomer used for imparting flame retardancy to various plastic materials, a method for producing the same, a phosphorus-containing polymer using the same, and a resin composition containing the same.

  Various plastic flame retardants are blended in plastic materials used when manufacturing various plastic products to impart flame retardancy. Conventionally, flame retardants can be achieved by blending compounds containing halogen elements. (See Patent Document 1). In the provision of such flame retardancy, in recent years, a method using a flame retardant containing no halogen-based material has been demanded from the viewpoint of avoiding environmental burdens. For example, phosphate esters, phosphazene compounds, magnesium hydroxide A technique of adding a metal hydroxide such as aluminum hydroxide as a flame retardant is mainly employed (see, for example, Patent Document 2).

JP 2001-42526 A JP 2005-283762 A

  However, the phosphorus compounds such as the phosphoric acid ester and the phosphazene compound are excellent in flame retardancy but are additive type flame retardants, and therefore have problems such as bleeding at high temperature and high pressure and precipitation at high temperature and high humidity. is doing. In addition, regarding the metal hydroxide, it is difficult to ensure desired flame retardancy unless it is added in a large amount, and therefore it is difficult to satisfy various properties other than flame retardancy by adding a large amount, etc. There was a problem.

  The present invention has been made in view of such circumstances, taking into consideration environmental aspects due to non-halogenation, has excellent flame retardancy, and can suppress the seepage and precipitation of flame retardant components. It is an object of the present invention to provide a monomer, a process for producing the same, a phosphorus-containing polymer using the monomer, and a resin composition containing the same.

In order to achieve the above object, the present invention has a first gist of a phosphorus-containing vinyl monomer represented by the following general formula (1).

And it is a method for producing the phosphorus-containing vinyl monomer, wherein the compound represented by the following general formula (3) and the compound represented by the following general formula (4) are reacted. A method for producing a monomer is a second gist.

Further, a phosphorus-containing polymer obtained by polymerizing an ethylenically unsaturated group-containing compound containing the phosphorus-containing vinyl monomer, the phosphorus-containing polymer containing a structural unit represented by the following general formula (2) Is the third gist.

  Moreover, let the resin composition containing the said phosphorus containing polymer be a 4th summary.

  That is, the present inventors use an ethylenically unsaturated group-containing phosphorus compound (phosphorus-containing monomer) as a reactive phosphorus-containing compound having flame retardancy, and copolymerize it with other ethylenically unsaturated group-containing compounds. Thus, a series of researches were repeated in order to produce a copolymer and to obtain a resin composition excellent in suppressing bleeding and precipitation. In the course of that research, we recalled the creation and use of a new compound, a phosphorus-containing vinyl monomer having the above specific structure. Then, using this specific phosphorus-containing vinyl monomer, this is copolymerized with another ethylenically unsaturated group-containing compound to produce a phosphorus-containing polymer that is a copolymer containing the specific structural unit. When this is used, it exhibits excellent flame retardancy because it contains a phosphorus atom in the side chain, and when used as a flame retardant component of various molding materials, the flame retardant component oozes out and precipitates from the molded body. It was found that it was suppressed and reached the present invention.

  In preparing the phosphorus-containing vinyl monomer of the present invention, the phosphorus-containing epoxy compound and the production method thereof disclosed in Japanese Patent Publication No. 4-39473 were referred to. According to the above publication, “When a phosphorus compound having a P—H group bond is reacted with a glycidyl ester compound containing a vinyl group, the P—H group is added to the vinyl group very selectively and quantitatively. It was found that it was difficult to cause an addition reaction with an epoxy group, and the present invention was completed. " With reference to this description, the present inventors made a reaction of a phosphorus-containing compound having a P—H bond with a compound having one ethylenically unsaturated group having a different structure in each molecule, a total of two, and the above 2 Recalling that it is possible to selectively carry out an addition reaction selectively with any one of the ethylenically unsaturated groups, the present invention has been achieved.

  Thus, the present invention is a phosphorus-containing vinyl monomer represented by the general formula (1). Moreover, it is a phosphorus-containing polymer obtained by polymerizing this phosphorus-containing vinyl monomer, and is a phosphorus-containing polymer containing the structural unit represented by the general formula (2). For this reason, while the said compound has the outstanding flame retardance by non-halogenation, when this is used as a flame retardant, it becomes possible to obtain the resin composition by which precipitation of the flame retardant component was suppressed.

  Such a phosphorus-containing vinyl monomer can be easily produced by reacting the compound represented by the general formula (3) with the general formula (4).

  The composition comprising the phosphorus-containing polymer of the present invention can be used for various molding materials. For example, it contains an ethylenically unsaturated group-containing polymerizable compound and a photopolymerization initiator together with the phosphorus-containing polymer. The use as a photosensitive resin composition containing is mentioned. Specifically, it can be used as a cover insulating layer forming material, and a flexible printed circuit board formed using the cover insulating layer is used as a mounting board by mounting electronic components, for example, a small device such as a mobile phone. It is used as a flexible printed circuit board.

  When the bisphenol A-based (meth) acrylate compound represented by the general formula (a) is used as the ethylenically unsaturated group-containing polymerizable compound, exposure sensitivity and development can be achieved when used as a photosensitive resin composition. Good quality can be obtained.

  Next, an embodiment for carrying out the present invention will be described in detail.

  The phosphorus-containing vinyl monomer of the present invention is a compound represented by the following general formula (1), and is effective in improving flame retardancy because it contains a phosphorus atom (P) in its molecular structure. In addition, since it contains an allyl group, it can be copolymerized with other ethylenically unsaturated group-containing compounds, and is particularly useful for various applications requiring flame retardancy.

In the above formula (1), as described in the production by addition reaction of the phosphorus-containing vinyl monomer represented by the following formula (1), among them, R ₁ and R ₂ are both hydrogen atoms, _A compound in which ₁ is a methyl group and X ₂ is a single bond is preferable. In the present invention, the term “single bond” means that —CH ₂ — and —O— which are bonded up and down via X ₂ are directly bonded in Formula (1) (same as Formula (4)). .

  That is, the phosphorus-containing vinyl monomer of the present invention can be produced, for example, as follows. First, a compound represented by the following general formula (3) and a compound represented by the following general formula (4) are prepared, and both are pressurized or normal pressure at a substantially molar ratio. It can be produced by heating under (101.3 kPa) to cause addition reaction.

  The heating conditions are preferably 100 to 200 ° C., more preferably 120 to 160 ° C., preferably 1 to 12 hours, and more preferably 2 to 10 hours.

  Further, as the pressurizing condition, specifically, it is preferably set to 0.1 to 0.5 MPa, more preferably 0.1 to 0.4 MPa.

  The above reaction can be carried out in an inert solvent as necessary. Examples of the inert solvent used in the above reaction include diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, solvent naphtha, N-methylpyrrolidone, γ-butyrolactone, butyl cellosolve, ethyl cellosolve, Examples include methyl cellosolve, toluene, xylene, propylene glycol monomethyl ether acetate and the like. These may be used alone or in combination of two or more.

Among the compounds represented by the general formula (3), those in which R ₁ and R ₂ are both hydrogen atoms are preferably used from the viewpoint of easy availability of materials. Of the compounds represented by the general formula (4), those in which X ₁ is a methyl group and X ₂ is a single bond are preferably used from the viewpoint of easy availability of materials. Therefore, in the general formula (1), which is the phosphorus-containing vinyl monomer of the present invention, it is preferable that R ₁ and R ₂ are both hydrogen atoms, X ₁ is a methyl group, and X ₂ is a single bond. It is.

  The phosphorus-containing vinyl monomer of the present invention is used to produce a phosphorus-containing polymer either alone or by copolymerizing with another ethylenically unsaturated group-containing compound. It contains a structural unit represented by the formula (2).

  As the other ethylenically unsaturated group-containing compound to be copolymerized with the phosphorus-containing vinyl monomer, various compounds can be used depending on applications. For example, alkyl esters of (meth) acrylic acid such as (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth ) Tetrahydrofurfuryl acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, styrene, α-styrene, vinyltoluene, N-vinylpyrrolidone, 2-hydroxyethyl (meth) acrylate, acrylamide, Examples include acrylonitrile, methacrylonitrile, N-phenylmaleimide, cyclohexylmaleimide, glycidyl (meth) acrylate, hydroxy (meth) acrylate, and the like. These may be used alone or in combination of two or more.

  Specifically, the phosphorus-containing polymer can be produced, for example, as follows. That is, in an inert atmosphere of the phosphorus-containing vinyl monomer obtained as described above in an inert atmosphere, the ethylenically unsaturated group-containing compound and, if necessary, a radical polymerization initiator and the like are appropriately added while heating. In addition, a phosphorus-containing polymer can be produced by copolymerizing both.

  As said heating conditions, Preferably it is set to the range of 50-160 degreeC, More preferably, it is 60-150 degreeC.

  The copolymerization ratio of the phosphorus-containing vinyl monomer and the ethylenically unsaturated group-containing compound is appropriately set depending on the application. For example, from the viewpoint of improving and imparting flame retardancy, the content of phosphorus atom (P) in the obtained phosphorus-containing polymer is preferably at least 1% by weight, more preferably at least 2% by weight. Thus, the copolymerization ratio of the two is set. When the phosphorus atom (P) content in the obtained phosphorus-containing polymer is too small, there is a tendency that sufficient flame retardancy is hardly obtained.

  The phosphorus-containing polymer obtained by using the phosphorus-containing vinyl monomer of the present invention is itself used as a flame retardant. Alternatively, other compounds may be added thereto and used as appropriate for various applications, for example, molding materials, film materials, adhesive materials, surface protective materials and the like.

  As said other compound, although it selects suitably according to a use, For example, a thermosetting compound, a photocurable compound, a thermosetting agent, a photocuring agent (photoinitiator), a thermosetting catalyst, photocuring Examples thereof include catalysts, other flame retardants (used within the range not impairing the effects of the present invention), fillers, plasticizers, colorants, solvents and the like.

  Next, a resin composition using a phosphorus-containing polymer obtained by using the phosphorus-containing vinyl monomer of the present invention will be described.

  The resin composition contains the phosphorus-containing polymer for imparting flame retardancy, and may further contain a phosphorus-containing vinyl monomer.

  The resin composition will be described by taking a photosensitive resin composition as an example.

  The said photosensitive resin composition is obtained using an ethylenically unsaturated group containing polymeric compound, a photoinitiator, and a thermosetting compound with the said phosphorus containing polymer, for example. Furthermore, in addition to these, the phosphorus-containing vinyl monomers described above can be used as flame retardant components.

  As the ethylenically unsaturated group-containing polymerizable compound used together with the phosphorus-containing polymer, for example, in consideration of the use of a photosensitive resin composition, it has a balance of properties such as solder heat resistance, folding resistance, and alkali developability. From the point which is excellent, the bisphenol A type | system | group di (meth) acrylate compound represented by the following general formula (a) is mention | raise | lifted.

  In the formula (a), examples of the alkylene group having 2 to 6 carbon atoms include an ethylene group, a propylene group, an isopropylene group, a butylene group, an isobutylene group, a pentylene group, a neopentylene group, and a hexylene group. In particular, an ethylene group is preferable.

The isopropylene group is a group represented by —CH (CH ₃ ) CH ₂ —, and is bonded to — (O—Y ¹ ) — and — (Y ² —O) — in the above general formula (a). There are two types of directions: a case where the methylene group is bonded to oxygen and a case where the methylene group is not bonded to oxygen. One direction may be used, or two types of bonding directions may be mixed. Good.

When the repeating units of-(O-Y ¹ )-and-(Y ² -O)-are each 2 or more, 2 or more Y ¹ and 2 or more Y ² may be the same or different from each other. May be. When Y ¹ and Y ² is composed of two or more alkylene groups, two or more of - (O-Y ¹⁾ - and - (Y ² -O) - may be present randomly However, it may exist in blocks.

  In the general formula (a), the substitutable positions of the two benzene rings may have one or more substituents, and in the case of having two or more substituents, These substituents may be the same as or different from each other. Examples of such a substituent include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an amino group, a nitro group, a cyano group, a mercapto group, An allyl group, an alkyl mercapto group having 1 to 10 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, a carboxyalkyl group having 1 to 10 carbon atoms in the alkyl group, an acyl group having 1 to 10 carbon atoms in the alkyl group, Examples thereof include an alkoxy group having 1 to 20 carbon atoms or a group containing a heterocyclic ring.

  In the general formula (a), the repeating numbers p and q are positive integers selected such that p + q is 4 to 40, and more preferably are positive integers selected so that p + q is 4 to 15. Particularly preferably, it is a positive integer selected such that p + q is 5 to 13. That is, if p + q is too small, the folding resistance tends to decrease. If p + q is too large, the entire photosensitive resin composition system is hydrophilic, and the insulation reliability under high temperature and high humidity is poor. This is because there is a tendency. Furthermore, the repetition number p is a positive number from 1 to 30.

  Examples of the bisphenol A-based di (meth) acrylate compound represented by the general formula (a) include 2,2′-bis [4- (meth) acryloxydiethoxyphenyl] propane and 2,2′-bis. [4- (meth) acryloxytetraethoxyphenyl] propane, 2,2′-bis [4- (meth) acryloxypentaethoxyphenyl] propane, 2,2′-bis [4- (meth) acryloxydiethoxy Octapropoxyphenyl] propane, 2,2′-bis [4- (meth) acryloxytriethoxyoctapropoxyphenyl] propane, and the like. These may be used alone or in combination of two or more. More specifically, BPE500 manufactured by Shin-Nakamura Chemical Co., Ltd. can be used.

  Next, examples of the photopolymerization initiator include substituted or unsubstituted polynuclear quinones (2-ethylanthraquinone, 2-t-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenyl. Anthraquinone), α-ketaldonyl alcohols (benzoin, pivalon, etc.), ethers, α-hydrocarbon-substituted aromatic acyloins (α-phenyl-benzoin, α, α-diethoxyacetophenones, etc.), aromatic Ketones (benzophenone, 4,4′-bisdialkylaminobenzophenone such as N, N′-tetraethyl-4,4′-diaminobenzophenone), thioxanthones (2-methylthioxanthone, 2,4-diethylthioxanthone, 2- Chlorthioxanthone, 2-isopropylthioxanthone And 2-methylthioxanthone), 2-methyl-1- [4- (methylthio) phenyl] -morpholinopropan-1-one and the like. These may be used alone or in combination of two or more.

  And as said thermosetting compound, it is preferable to use an epoxy compound, block isocyanate, etc., for example.

  As the above-mentioned epoxy compound, it is preferable to use a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, or the like from the viewpoint of heat resistance and flexibility in consideration of its use. Among these, it is particularly preferable to use a bisphenol A type epoxy resin from the viewpoint of a balance between heat resistance and flexibility.

  Moreover, as said blocked isocyanate, specifically, Sumidur BL-3175, BL-1100, BL-3272, BL-1265, etc. by Sumika Bayer Urethane Co., Ltd. are used.

  Content of each said component in the photosensitive resin composition is set as follows. First, it is preferable to set content of the said phosphorus containing polymer to the range of 30 to 70 weight% of the whole photosensitive resin composition, More preferably, it is 35 to 65 weight%. That is, when the content of the phosphorus-containing polymer is too small, a tendency to be inferior in flame retardancy is observed, and when the content is too large, a tendency to be inferior in heat resistance is observed.

  The content of the ethylenically unsaturated group-containing polymerizable compound is preferably set in the range of 3 to 30% by weight, more preferably 5 to 25% by weight of the entire photosensitive resin composition. That is, if the content of the ethylenically unsaturated group-containing polymerizable compound is too small, the sensitivity upon exposure to the photosensitive resin composition tends to deteriorate, and if the content is too large, alkali developability This is because the tendency to decrease is observed.

  The content of the photopolymerization initiator is preferably set in the range of 0.2 to 10% by weight of the entire photosensitive resin composition, and more preferably 0.5 to 8% by weight. That is, if the content of the photopolymerization initiator is too small, the sensitivity tends to be insufficient, and if the content is too large, the alkali developability tends to decrease.

  The content of the thermosetting compound is preferably set in the range of 3 to 40% by weight, more preferably 5 to 30% by weight, based on the entire nonvolatile components of the photosensitive resin composition. That is, if the content of the thermosetting compound is too small, the heat resistance tends to be insufficient, and if the content is too large, the developability tends to decrease.

  In addition to the above components, the photosensitive resin composition may contain other additives as necessary, that is, pigments such as phthalocyanine green and phthalocyanine blue, fillers such as silica, barium sulfate, and talc, antifoaming Agents, leveling agents, other flame retardants, stabilizers, adhesion-imparting agents such as 2-amino-5-mercapto-1,3,4-thiadiazole and 5-amino-1-H-tetrazole, and prevention of benzotriazole and the like A rusting agent etc. can be mix | blended suitably. These may be used alone or in combination of two or more. And it is preferable to use these other additives within the range of 0.01-30 weight% of the whole photosensitive resin composition.

  The said photosensitive resin composition is obtained by mix | blending and mixing each said component so that it may become predetermined | prescribed content. And the said photosensitive resin composition can be mixed and used for an organic solvent as needed. Examples of the organic solvent include diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, solvent naphtha, N-methylpyrrolidone, γ-butyrolactone, butyl cellosolve, ethyl cellosolve, methyl cellosolve, toluene, A solvent such as xylene, mesitylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, or a mixed solvent thereof can be used.

  When using the said organic solvent, about 0-200 weight part can be mixed and used with respect to 100 weight part of photosensitive resin compositions, for example.

  The photosensitive resin composition is useful as a solder resist (cover insulating layer forming material) for a printed circuit board such as a flexible printed circuit board, and also used for applications such as paints, coating agents, and adhesives. Can do.

  When using the said photosensitive resin composition as a soldering resist (cover insulating layer forming material) for flexible printed wiring circuit boards, it is used as follows, for example. In the following, description will be given in order.

  First, a flexible printed circuit board on which a predetermined conductor circuit pattern is formed is prepared. Then, the photosensitive resin composition is formed on the conductive circuit pattern forming surface of the flexible printed circuit board by a screen printing method, a spray method, a roll coating method, an electrostatic coating method or the like so that the thickness after drying becomes 5 to 50 μm. After applying the product and drying at 50 to 160 ° C. for about 1 to 60 minutes, a negative or positive pattern mask film is placed in direct contact with or without contact with the coating film, and then irradiated with actinic rays To do.

  Alternatively, the photosensitive resin composition is applied and dried on a transparent support film such as polyethylene terephthalate (PET) so that the thickness after drying becomes 5 to 50 μm, and the polyethylene or the like is applied on the dried photosensitive resin composition. The laminated body containing the photosensitive resin composition is produced by bonding the protective film.

  Next, after peeling off the protective film of the laminate, it is bonded to the conductive circuit pattern forming surface of the flexible printed circuit board, and the mask film is placed in direct contact with the transparent support film or without contact. Then, after irradiating with actinic rays, the transparent support film of the laminate is peeled off.

As the actinic light source, various known light sources such as a carbon arc lamp, a mercury vapor arc lamp, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, and a metal hydride lamp are used. Moreover, what irradiates visible light effectively, such as a photographic flood light bulb and a solar lamp, is also used. In addition, as said irradiation conditions of actinic light, it is preferable to set to about 10-1000 mJ / cm < ² >, for example.

  Next, using a developing solution such as an alkaline aqueous solution, the unexposed portion is removed and developed by a known method such as spraying, rocking dipping, brushing, scraping, etc. to produce a resist pattern.

  Examples of the alkaline aqueous solution used for the development include a dilute solution of 0.1 to 5 wt% sodium carbonate, a dilute solution of 0.1 to 5 wt% potassium carbonate, a dilute solution of 0.1 to 5 wt% sodium hydroxide, 0 A dilute solution of 1 to 5% by weight sodium tetraborate or the like can be used.

Next, after the development, a crosslinking reaction by heating is performed for the purpose of improving solder heat resistance, chemical resistance and the like. As said heating conditions, it is preferable to carry out for about 1 to 10 hours in the range of about 100-260 degreeC. Furthermore, in addition to the above heating, ultraviolet irradiation with a high-pressure mercury lamp or a low-pressure mercury lamp can be performed before or after the heating, if necessary. The irradiation amount of the ultraviolet rays is preferably set to about 0.2 to 10 J / cm ² .

  In this way, a flexible printed circuit board having a solder resist (cover insulating layer) formed on the conductor circuit pattern is obtained. The flexible printed wiring circuit board on which the solder resist (cover insulating layer) is formed is then mounted by mounting electronic components such as LSI, diodes, transistors, capacitors, etc. by soldering or the like. It will be attached to small devices such as telephones.

  Next, examples will be described together with comparative examples. However, the present invention is not limited to these examples.

  First, a phosphorus-containing vinyl monomer was synthesized according to the following.

[Example 1]
[Synthesis of phosphorus-containing vinyl monomers (addition reaction)]
100 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 158.4 g of diethylene glycol monoethyl ether acetate are placed in a 500 ml separable flask under a nitrogen atmosphere and heated with stirring. Dissolved and heated to 140 ° C. To this, 58.4 g of allyl methacrylate was added dropwise over 2 hours, and the reaction was continued at 140 ° C. for 3 hours after the completion of the addition, whereby 9,10-dihydro-9-oxa- was added to the methacryloyl group of allyl methacrylate. A diethylene glycol monoethyl ether acetate solution (solid content concentration 50% by weight) of the compound to which 10-phosphaphenanthrene-10-oxide was added (reaction solution α) was prepared.

When the obtained compound was analyzed with a Fourier transform infrared spectrophotometer (FT-IR), the peak near 1620 cm ⁻¹ due to the methacryloyl group disappeared, and the peak near 1635 cm ⁻¹ due to the allyl group remained. Confirmed that. Further, when the molecular weight of the obtained compound was measured by gel permeation chromatography (GPC), only the peak corresponding to the molecular weight 342 was detected (the peak corresponding to the molecular weight 176 which is the molecular weight of the reaction solvent was excluded).

From these results, the obtained compound is a compound having the general formula (1) in which X ₁ is CH ₃ , R ₁ and R ₂ are both H, m and n are both 4, and X ₂ is a single bond (molecular weight 342).

[Example 2]
[Synthesis of phosphorus-containing polymer a]
Reaction solution α prepared by the above addition reaction [diethylene glycol monoethyl ether acetate solution of a compound in which 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is added to the methacryloyl group of allyl methacrylate] 132. 4 g (solid content: 66.2 g) and 33.8 g of propylene glycol monomethyl ether acetate were placed in a 500 ml separable flask under a nitrogen atmosphere and heated to 100 ° C. with stirring. To this, 20 g of methacrylic acid, 13.8 g of butyl acrylate and 1.6 g of azobisisobutyronitrile (radical polymerization initiator) were mixed and dissolved in a nitrogen atmosphere over 6 hours. By continuing stirring for 2 hours in a nitrogen atmosphere while maintaining 100 ° C., a solution of a phosphorus-containing polymer a was obtained [solid content 50% by weight, carboxylic acid equivalent calculated value: 430, phosphorus atom (P) content calculation Value: 6%, weight average molecular weight: 40,000].

[Comparative Example 1]
[Synthesis of polymerized product b]
40 g of methyl methacrylate, 20 g of methacrylic acid, 40 g of butyl acrylate, 100 g of propylene glycol monomethyl ether acetate and 1.6 g of azobisisobutyronitrile (radical polymerization initiator) are placed in a 300 ml separable flask under a nitrogen atmosphere and stirred. The solution was heated at 100 ° C. for 5 hours to obtain a carboxyl group-containing linear polymer (polymer b) solution (solid content: 50% by weight) [Carboxylic acid of carboxyl group-containing linear polymer] Equivalent calculation value: 430, phosphorus atom (P) content calculation value: 0%, weight average molecular weight: 40000].

  Using the phosphorus-containing polymer a of Example 2 and the polymer b of Comparative Example 1 obtained as described above, and preparing the components shown below, the composition shown in Table 1 below is prepared. A photosensitive resin composition was prepared by mixing the components. In addition, the compounding quantity of the mixing | blending component in Table 1 shows the weight part of a non volatile matter, and the sum total of a mixing | blending component amount will be 100 weight part.

[Ethylenically unsaturated group-containing polymerizable compound]
Ethylene oxide-modified bisphenol A methacrylate [p + q = 10 in the above formula (a), BIS-A acrylate: manufactured by Shin-Nakamura Chemical Co., BPE500]
[Flame retardant b]
Cyclic phosphazene oligomer (Otsuka Chemical Co., Ltd., SPB-100)
(Photopolymerization initiator)
Irgacure369, manufactured by Ciba Geigy
[Epoxy compound]
JER1055 (bisphenol A type epoxy resin) manufactured by Japan Epoxy Resin Co., Ltd.
[Adhesion imparting agent]
5-Amino-1-H-tetrazole

  The characteristic evaluation of the obtained photosensitive resin composition was performed according to the following method, and the results are also shown in Table 1 below.

〔Flame retardance〕
Each photosensitive resin composition solution is applied to one side of a polyimide film having a thickness of 25 μm and dried (80 ° C. × 30 minutes) so that the film thickness after drying is 20 μm. A 38 μm surface-treated polyethylene terephthalate (PET) cover film was adhered to produce a laminate. Subsequently, the laminate was irradiated with ultraviolet rays with an exposure amount of 300 mJ / cm ^{2 using} a 250 W ultrahigh pressure mercury lamp. Thereafter, the cover film is peeled off, developed with a 1 wt% sodium carbonate aqueous solution at 30 ° C. for 90 seconds at a pressure of 0.2 MPa, further washed with tap water for 30 seconds, and then with a hot air circulation dryer. Heat treatment was performed at 150 ° C. for 8 hours.

  Similarly, a film of the photosensitive resin composition was formed on the back surface of the polyimide film. This was evaluated for flame retardancy according to an apparatus (UL combustion test chamber, manufactured by Toyo Seiki Co., Ltd.) and method (VTM method) based on flame retardancy test standard UL94. As shown in Table 1 below, “VTM-0” was determined to be acceptable in the flame retardancy test.

[Deposition of flame retardant]
Each photosensitive resin composition solution is applied to one side of a polyimide film having a thickness of 25 μm and dried (80 ° C. × 30 minutes) so that the film thickness after drying is 20 μm. A 38 μm surface-treated polyethylene terephthalate (PET) cover film was adhered to produce a laminate. Subsequently, the laminate was irradiated with ultraviolet rays with an exposure amount of 300 mJ / cm ^{2 using} a 250 W ultrahigh pressure mercury lamp. Thereafter, the cover film is peeled off, developed with a 1 wt% sodium carbonate aqueous solution at 30 ° C. for 90 seconds at a pressure of 0.2 MPa, further washed with tap water for 30 seconds, and then with a hot air circulation dryer. A sample was prepared by heat treatment at 150 ° C. for 8 hours.

The sample was put into a constant temperature and humidity chamber of 65 ° C. × 95% RH, and the surface of the sample after 1000 hours was visually observed using a microscope with a magnification of 50 times and evaluated according to the following criteria.
A: No precipitate was confirmed on the sample surface.
X: Precipitates were confirmed on the sample surface.
In addition, when the deposit confirmed on the sample surface using the photosensitive resin composition of the comparative example 1 was analyzed using FT-IR, SPB-100 which is a flame retardant component (manufactured by Otsuka Chemical Co., Ltd., cyclic phosphazene oligomer) ) And the peak were almost the same.

  From the said result, while Example 2 using the phosphorus containing polymer a shows the outstanding flame retardance, precipitation of a flame retardant component is not confirmed but it turns out that precipitation of a flame retardant was suppressed effectively. On the other hand, in Comparative Example 1 using the polymer b, there was no problem with respect to the flame retardancy and the flame retardancy equivalent to that of the Example was obtained, but the flame retardant component was precipitated.

  The phosphorus-containing vinyl monomer of the present invention is excellent in flame retardancy, and can be used as a flame retardant component as a blending component of various molding materials. For example, a photosensitive resin composition containing this phosphorus-containing polymer is prepared and useful as a cover insulating layer forming material for a flexible printed circuit board.

Claims (7)

A phosphorus-containing vinyl monomer represented by the following general formula (1).

A method for producing a phosphorus-containing vinyl monomer represented by the general formula (1) according to claim 1, wherein the compound is represented by the following general formula (3) and the following general formula (4). A method for producing a phosphorus-containing vinyl monomer characterized by reacting with a compound to be produced.

A phosphorus-containing polymer obtained by polymerizing an ethylenically unsaturated group-containing compound containing a phosphorus-containing vinyl monomer represented by the general formula (1) according to claim 1, which is represented by the following general formula (2): A phosphorus-containing polymer, characterized by containing a structural unit.

  The phosphorus-containing polymer according to claim 3, wherein the ethylenically unsaturated group-containing compound contains at least one of (meth) acrylic acid and an alkyl ester of (meth) acrylic acid.   A resin composition comprising the phosphorus-containing polymer according to claim 3 or 4.   Furthermore, the resin composition of Claim 5 which is a photosensitive resin composition containing an ethylenically unsaturated group containing polymeric compound and a photoinitiator. The resin composition according to claim 6, wherein the ethylenically unsaturated group-containing polymerizable compound is a bisphenol A di (meth) acrylate compound represented by the following general formula (a).