TWI658325B - Photosensitive resin composition, dry film, cured product, and printed wiring board - Google Patents
Photosensitive resin composition, dry film, cured product, and printed wiring board Download PDFInfo
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Abstract
本發明之課題為提供一種在硬化物上難以產生磨擦痕跡的感光性樹脂組成物、塗布並乾燥該組成物而成之乾膜、該組成物或該乾膜之硬化物以及具有該硬化物之印刷配線板。 An object of the present invention is to provide a photosensitive resin composition which is hard to produce abrasion marks on a cured product, a dry film obtained by coating and drying the composition, a cured product of the composition or the dried film, and a cured product having the cured product. Printed wiring board.
作為解決手段,本發明為提供一種感光性樹脂組成物,其特徵為包含(A)含有羧基之樹脂、(B)官能基數為6個以上的氨基甲酸乙酯(甲基)丙烯酸酯、(C)光聚合起始劑以及(D)氧化鈦。且前述(B)官能基數為6個以上的氨基甲酸乙酯(甲基)丙烯酸酯之重量平均分子量為1,500~200,000較佳。 As a solution, the present invention is to provide a photosensitive resin composition characterized by including (A) a carboxyl group-containing resin, (B) a urethane (meth) acrylate having 6 or more functional groups, and (C ) Photopolymerization initiator and (D) titanium oxide. The weight average molecular weight of the urethane (meth) acrylate having 6 or more (B) functional groups is preferably 1,500 to 200,000.
Description
本發明為關於一種感光性樹脂組成物、乾膜、硬化物以及印刷配線板,詳細來說,是關於一種在硬化物上難以產生磨擦痕跡之感光性樹脂組成物、塗布並乾燥該組成物而成之乾膜、該組成物或該乾膜之硬化物以及具有該硬化物之印刷配線板。 The present invention relates to a photosensitive resin composition, a dry film, a cured product, and a printed wiring board. In particular, the present invention relates to a photosensitive resin composition which is hard to produce abrasion marks on the cured product, and the composition is coated and dried. The resulting dry film, the composition or a cured product of the dried film, and a printed wiring board having the cured product.
藉由將感光性樹脂組成物塗布於印刷配線板等基材上並進行光硬化,作為阻焊等絕緣層來使用廣泛地被進行(例如專利文獻1)。光硬化性組成物被利用來作為裝載有發光二極管(LED)、電致發光(EL)等發光元件之印刷配線板中的絕緣層時,為了能夠有效利用光,較多是由高反射率的白色感光性樹脂組成物所構成(例如專利文獻2)。 A photosensitive resin composition is applied to a substrate such as a printed wiring board and photocured, and is widely used as an insulating layer such as solder resist (for example, Patent Document 1). When a photocurable composition is used as an insulating layer in a printed wiring board on which light emitting elements such as light emitting diodes (LEDs) and electroluminescence (EL) are mounted, in order to make efficient use of light, high reflectivity is often used. A white photosensitive resin composition (for example, Patent Document 2).
[專利文獻1]日本特開2005-311233號公報 [Patent Document 1] Japanese Patent Laid-Open No. 2005-311233
[專利文獻2]日本特開2010-160471號公報 [Patent Document 2] Japanese Patent Laid-Open No. 2010-160471
由於印刷配線板或電子機器之製造時,印刷配線板的堆疊或印刷配線板與搬送滾輪的接觸等,有時設置在印刷配線板上的阻焊等之絕緣層會與銅等金屬接觸。且,若是設置在可繞式配線板上的阻焊,將零件裝載於電子機器內時,有時也會圍繞在金屬上。若為了得到高反射率的白色阻焊而高度填充氧化鈦的話,由於在如此般製造時或實用時與金屬之接觸,會有在阻焊上產生磨擦痕跡之問題。 When a printed wiring board or an electronic device is manufactured, the printed wiring board is stacked, or the printed wiring board is in contact with a conveying roller, etc., and an insulating layer such as a solder resist provided on the printed wiring board may come into contact with a metal such as copper. In addition, in the case of a solder resist provided on a windable wiring board, when a component is mounted in an electronic device, it may be surrounded by a metal. If titanium oxide is highly filled in order to obtain a white solder mask having a high reflectance, there is a problem that abrasion marks are generated on the solder mask due to contact with a metal during such manufacturing or practical use.
於此,本發明之目的為提供一種在硬化物上難以產生磨擦痕跡之感光性樹脂組成物、塗布並乾燥該組成物而成之乾膜、該組成物或該乾膜之硬化物以及具有該硬化物之印刷配線板。 Herein, an object of the present invention is to provide a photosensitive resin composition which is hard to produce abrasion marks on a cured product, a dry film formed by coating and drying the composition, the composition or a cured product of the dry film, and Hardened printed wiring board.
本發明者等為了解決上述課題進行縝密探討之結果發現藉由於感光性樹脂組成物中含有官能基數為6個以上的氨基甲酸乙酯(甲基)丙烯酸酯,能夠解決上述課題,進而完成本發明。 The present inventors conducted intensive studies in order to solve the above-mentioned problems, and found that the photosensitive resin composition contains a urethane (meth) acrylate having 6 or more functional groups, which can solve the above-mentioned problems, thereby completing the present invention. .
亦即,本發明之感光性樹脂組成物,其特徵為包含(A)含有羧基之樹脂、(B)官能基數為6個以上的氨 基甲酸乙酯(甲基)丙烯酸酯、(C)光聚合起始劑以及(D)氧化鈦。 That is, the photosensitive resin composition of the present invention is characterized by including (A) a resin containing a carboxyl group, and (B) ammonia having 6 or more functional groups. Urethane (meth) acrylate, (C) a photopolymerization initiator, and (D) titanium oxide.
本發明之感光性樹脂組成物中,前述(B)官能基數為6個以上的氨基甲酸乙酯(甲基)丙烯酸酯之重量平均分子量為1,500~200,000較佳。 In the photosensitive resin composition of the present invention, the weight average molecular weight of the urethane (meth) acrylate having 6 or more functional groups (B) is preferably 1,500 to 200,000.
本發明之感光性樹脂組成物中,進一步包含金屬氫氧化物以及磷系化合物中至少任1種較佳。 The photosensitive resin composition of the present invention preferably further contains at least any one of a metal hydroxide and a phosphorus compound.
本發明之乾膜,其特徵為在薄膜上塗布前述感光性樹脂組成物並使其乾燥而成。 The dry film of the present invention is characterized in that the photosensitive resin composition is coated on a film and dried.
本發明之硬化物,其特徵為將前述感光性樹脂組成物或前述乾膜硬化所得。 The cured product of the present invention is obtained by curing the photosensitive resin composition or the dry film.
本發明之印刷配線板,其特徵為具有前述硬化物。 The printed wiring board of the present invention is characterized by having the aforementioned hardened material.
藉由本發明,能夠提供一種解像性、硬化物之折疊性優異,且在硬化物上難以產生磨擦痕跡之感光性樹脂組成物、塗布該組成物並使其乾燥所得之乾膜、該組成物或該乾膜之硬化物以及具有該硬化物之印刷配線板。 According to the present invention, it is possible to provide a photosensitive resin composition which is excellent in resolvability and foldability of a cured product, and hardly produces friction marks on the cured product, a dried film obtained by coating the composition, and drying the composition, and the composition. Or hardened matter of the dry film and printed wiring board having the hardened matter.
本發明之感光性樹脂組成物之特徵為包含(A)含有羧基之樹脂、(B)官能基數為6個以上的氨基甲酸乙酯(甲基)丙烯酸酯(以下,單純稱作「(B)氨基甲酸乙酯(甲 基)丙烯酸酯」)、(C)光聚合起始劑以及(D)氧化鈦。硬化物所產生的磨擦痕跡被認為是由於氧化鈦的硬度較高,故因為與金屬之磨擦,被露出在阻焊表面的氧化鈦刮到的金屬附著在阻焊表面上者。本發明中,認為藉由(B)官能基數為6個以上的氨基甲酸乙酯(甲基)丙烯酸酯之摻混,硬化物的表面硬度會提升,磨擦所造成的氧化鈦露出會降低,故磨擦痕跡較難以產生(以下亦稱為「耐刮痕性優異」)。且,作為提升表面硬度的其他手段,認為有增加光聚合起始劑或光聚合性單體的摻混量,但本發明之感光性樹脂組成物所得之硬化物,在此等之手段中會惡化的解像性或硬化物的折疊性都較優異。且,填充氧化鈦的話,光澤度會降低,但本發明之感光性樹脂組成物所得之硬化物其光澤度亦良好。於此,「(甲基)丙烯酸酯」意指總稱丙烯酸酯、丙烯酸甲酯以及此等之混合物之用語,關於本說明書中其他類似的表現也是相同的。以下,關於各成分進行詳細地說明。 The photosensitive resin composition of the present invention is characterized by including (A) a carboxyl group-containing resin and (B) a urethane (meth) acrylate having 6 or more functional groups (hereinafter, simply referred to as "(B) Urethane Group) acrylate "), (C) a photopolymerization initiator, and (D) titanium oxide. The friction marks produced by the hardened material are considered to be due to the high hardness of the titanium oxide. Therefore, due to the friction with the metal, the metal scraped by the titanium oxide exposed on the solder resist surface adheres to the solder resist surface. In the present invention, it is considered that by blending a urethane (meth) acrylate having 6 or more functional groups, the hardness of the surface of the hardened product will be increased, and the exposure of titanium oxide due to friction will be reduced. Friction marks are less likely to occur (hereinafter also referred to as "excellent scratch resistance"). In addition, as another means for improving the surface hardness, it is considered that the blending amount of the photopolymerization initiator or the photopolymerizable monomer is increased. However, the hardened material obtained by the photosensitive resin composition of the present invention may be increased by these means. Both the deteriorated resolution and the foldability of the cured product are excellent. In addition, when titanium oxide is filled, the gloss decreases, but the cured product obtained from the photosensitive resin composition of the present invention also has good gloss. Herein, "(meth) acrylate" means the general term of acrylate, methyl acrylate, and mixtures thereof, and other similar expressions in this specification are also the same. Hereinafter, each component is demonstrated in detail.
作為上述(A)含有羧基之樹脂,能夠使用包含周知的羧基之樹脂。藉由羧基的存在,能夠將樹脂組成物成為鹼顯像性。且,以將本發明之感光性樹脂組成物成為光硬化性或耐顯像性之觀點來看,除了羧基,分子內具有乙烯性不飽和鍵結較佳,但能夠僅將不具有乙烯性不飽和雙鍵的含有羧基之樹脂作為(A)成分來使用。作為乙烯性不飽和 雙鍵,以丙烯酸或甲基丙烯酸或來自此等之衍生物者較佳。(A)含有羧基之樹脂能夠使用單獨1種或組合2種以上來使用。 As the (A) carboxyl group-containing resin, a resin containing a well-known carboxyl group can be used. By the presence of a carboxyl group, the resin composition can be made alkali developable. In addition, from the viewpoint of making the photosensitive resin composition of the present invention photocurable or developable, it is preferable to have an ethylenically unsaturated bond in the molecule in addition to the carboxyl group. A carboxyl group-containing resin having a saturated double bond is used as the component (A). As ethylenically unsaturated The double bond is preferably acrylic acid or methacrylic acid or a derivative derived therefrom. (A) A carboxyl group-containing resin can be used individually by 1 type or in combination of 2 or more types.
作為本發明之感光性樹脂組成物中能夠使用的含有羧基之樹脂之具體例,有舉出如以下所列舉的化合物(寡聚物以及聚合物之任一者皆可)。 Specific examples of the carboxyl group-containing resin that can be used in the photosensitive resin composition of the present invention include the following compounds (either an oligomer or a polymer may be used).
(1)(甲基)丙烯酸等之不飽和羧酸與苯乙烯、α-甲基苯乙烯、低級烷(甲基)丙烯酸酯、異丁烯等含有不飽和基之化合物共聚合所得之含有羧基之樹脂。 (1) Carboxyl-containing resins obtained by copolymerizing unsaturated carboxylic acids such as (meth) acrylic acid with unsaturated group-containing compounds such as styrene, α-methylstyrene, lower alkyl (meth) acrylates, and isobutylene .
(2)脂肪族二異氰酸酯、分支脂肪族二異氰酸酯、脂環式二異氰酸酯、芳香族二異氰酸酯等之二異氰酸酯與二羥甲基丙酸、二羥甲基丁酸等之含有羧基之二乙醇化合物以及具有聚碳酸酯系多元醇、聚醚系多元醇、聚酯系多元醇、聚烯烴系多元醇、丙烯系多元醇、雙酚A系環氧烷加成物二醇、苯酚性羥基以及醇性羥基之化合物等之二醇化合物之加成聚合反應所成的含有羧基之氨基甲酸乙酯樹脂。 (2) Carboxy-containing diethanol compounds such as diisocyanates of aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, and dimethylolpropionic acid, dimethylolbutyric acid And it has polycarbonate polyol, polyether polyol, polyester polyol, polyolefin polyol, propylene polyol, bisphenol A alkylene oxide adduct glycol, phenolic hydroxyl group and alcohol Carboxyl-containing urethane resin formed by addition polymerization of a diol compound such as a hydroxy compound.
(3)脂肪族二異氰酸酯、分支脂肪族二異氰酸酯、脂環式二異氰酸酯、芳香族二異氰酸酯等之二異氰酸酯化合物與具有聚碳酸酯系多元醇、聚醚系多元醇、聚酯系多元醇、聚烯烴系多元醇、丙烯系多元醇、雙酚A系環氧烷加成物二醇、苯酚性羥基以及醇性羥基之化合物等之二醇化合物之加成聚合反應所成的在氨基甲酸乙酯樹脂之末端使酸酐反應而成之末端含有羧基之氨基甲酸乙酯樹 脂。 (3) Diisocyanate compounds such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, etc., and having polycarbonate polyols, polyether polyols, polyester polyols, Polyurethane-based polyols, propylene-based polyols, bisphenol A-based alkylene oxide adduct glycols, phenolic hydroxyl groups, and alcoholic hydroxyl compounds such as glycol compounds Urethane tree fat.
(4)二異氰酸酯與雙酚A型環氧樹脂、氫化雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、雙二甲苯酚型環氧樹脂、雙苯酚型環氧樹脂等之2官能環氧樹脂之(甲基)丙烯酸酯或其部分酸酐改質物、含有羧基之二乙醇化合物以及二醇化合物之加成聚合反應所成之感光性含有羧基之氨基甲酸乙酯樹脂。 (4) Diisocyanate and bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisxylenol epoxy resin, bisphenol (Meth) acrylic acid esters of bifunctional epoxy resins such as type epoxy resins or modified anhydrides thereof, photosensitive carboxyl group-containing carbamic acid formed by addition polymerization reaction of carboxyl-containing diethanol compounds and glycol compounds Ethyl resin.
(5)上述(2)或(4)的樹脂合成中,添加羥烷基(甲基)丙烯酸酯等之在分子中具有1個羥基與1個以上(甲基)丙烯醯基之化合物,且進行末端(甲基)丙烯化之含有羧基之氨基甲酸乙酯樹脂。 (5) In the resin synthesis of the above (2) or (4), a compound having one hydroxyl group and one or more (meth) acrylfluorenyl groups in a molecule, such as a hydroxyalkyl (meth) acrylate, is added, and Carboxyl-containing urethane resin subjected to terminal (meth) acrylation.
(6)上述(2)或(4)之樹脂合成中,添加異佛酮二異氰酸酯與季戊四醇三丙烯酸酯之等莫耳反應物等,在分子中具有1個異氰酸酯基與1個以上(甲基)丙烯醯基之化合物,且進行末端(甲基)丙烯化之含有羧基之氨基甲酸乙酯樹脂。 (6) In the resin synthesis of the above (2) or (4), a mole reactant such as isophorone diisocyanate and pentaerythritol triacrylate is added, and the molecule has one isocyanate group and one or more (methyl groups) ) A compound of acrylfluorenyl group and a carboxyl group-containing urethane resin subjected to terminal (meth) acrylation.
(7)將如後述之多官能環氧樹脂與(甲基)丙烯酸反應,並對存在於側鏈上的羥基附加鄰苯二甲酐、四氫鄰苯二甲酐、六氫鄰苯二甲酐等二元酸酐後之感光性含有羧基之樹脂。於此,多官能環氧樹脂亦可為固體亦可為液狀。 (7) A polyfunctional epoxy resin as described below is reacted with (meth) acrylic acid, and phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic acid are added to the hydroxyl groups present on the side chains. A photosensitive carboxyl group-containing resin after a dibasic acid anhydride such as an anhydride. Here, the polyfunctional epoxy resin may be solid or liquid.
(8)將2官能環氧樹脂之羥基進一步以表氯醇進行環氧化之多官能環氧樹脂與(甲基)丙烯酸進行反應,對所產生之羥基上附加二元酸酐之感光性含有羧基之樹 脂。於此,2官能環氧樹脂亦可為固體亦可為液狀。 (8) The hydroxyl group of the bifunctional epoxy resin is further epoxidized with epichlorohydrin, and the polyfunctional epoxy resin is reacted with (meth) acrylic acid. tree fat. Here, the bifunctional epoxy resin may be solid or liquid.
(9)將如後述之多官能環氧丙烷樹脂與二羧酸反應,對所產生的1級羥基上附加二元酸酐之含有羧基之聚酯樹脂。 (9) A polyester resin containing a carboxyl group, in which a polyfunctional propylene oxide resin as described later is reacted with a dicarboxylic acid, and a dibasic acid anhydride is added to the generated primary hydroxyl group.
(10)使1分子中具有複數苯酚性羥基之化合物與環氧乙烷、環氧丙烯等之環氧烷反應所得之反應生成物與含有不飽和基之單羧酸反應,將所得之反應生成物與多元酸酐反應所得之含有羧基之感光性樹脂。 (10) A reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide is reacted with a monocarboxylic acid containing an unsaturated group, and the obtained reaction is formed into A carboxyl group-containing photosensitive resin obtained by reacting a substance with a polybasic acid anhydride.
(11)將1分子中具有複數苯酚性羥基之化合物與碳酸伸乙酯、碳酸丙烯酯等之環狀碳酸鹽化合物反應所得之反應生成物與含有不飽和基之單羧酸反應,再將所得之反應生成物與多元酸酐反應所得之含有羧基之感光性樹脂。 (11) A reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate, propylene carbonate, etc., and a monocarboxylic acid containing an unsaturated group, and then the obtained A carboxyl group-containing photosensitive resin obtained by reacting a reaction product with a polybasic acid anhydride.
(12)將1分子中具有複數環氧基之環氧化合物、與p-羥基苯乙醇等之1分子中具有至少1個醇性羥基與1個苯酚性羥基之化合物、與(甲基)丙烯酸等之含有不飽和基之單羧酸反應,並對所得之反應生成物之醇性羥基與馬來酸酐、四氫鄰苯二甲酐、苯偏三酸酐、苯均四酸酐、己二酸等之多元酸酐反應所得之含有羧基之感光性樹脂。 (12) An epoxy compound having a plurality of epoxy groups in one molecule, a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule and p-hydroxyphenylethanol, etc., and (meth) acrylic acid Monocarboxylic acids containing unsaturated groups are reacted, and the alcoholic hydroxyl groups of the obtained reaction products are reacted with maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic acid, etc. A carboxyl group-containing photosensitive resin obtained by reaction of a polybasic acid anhydride.
(13)進一步對上述(1)~(12)中任一者之樹脂附加環氧丙基(甲基)丙烯酸酯、α-甲基環氧丙基(甲基)丙烯酸酯等之分子中具有1個環氧基與1個以上(甲基)丙烯醯基之化合物所成之感光性含有羧基之樹脂。 (13) A molecule having epoxy propyl (meth) acrylate, α-methyl epoxy propyl (meth) acrylate, etc. added to the resin of any one of (1) to (12) above A photosensitive carboxyl group-containing resin formed from a compound having one epoxy group and one or more (meth) acrylfluorenyl groups.
如上述之含有羧基之樹脂由於在骨架.聚合物的側鏈上具有多數羧基,故能夠以稀鹼水溶液來顯像。 As mentioned above, the resin containing carboxyl group is in the skeleton. Since the polymer has a large number of carboxyl groups on its side chain, it can be developed with a dilute aqueous alkali solution.
且,(A)含有羧基之樹脂的酸價較期望為20~200mgKOH/g之範圍,再較佳為40~150mgKOH/g之範圍。含有羧基之樹脂的酸價在20mgKOH/g以上時,塗膜的密著性良好,且,鹼顯像也變得良好。另一方面,酸價為200mgKOH/g以下時,會抑制顯像液所造成的曝光部之溶解,必要以上會使線條變細,根據不同情況,能夠不分曝光部與未曝光部地抑制因顯像液的溶解剝離,並良好地描繪出光阻圖型。 The acid value of the (A) carboxyl group-containing resin is preferably in the range of 20 to 200 mgKOH / g, and more preferably in the range of 40 to 150 mgKOH / g. When the acid value of the carboxyl group-containing resin is 20 mgKOH / g or more, the adhesion of the coating film is good, and alkali development is also good. On the other hand, when the acid value is 200 mgKOH / g or less, the dissolution of the exposed portion caused by the developing solution is suppressed. If necessary, the lines become thinner. Depending on the situation, the factors can be suppressed regardless of the exposed portion and the unexposed portion. The developer is dissolved and peeled off, and the photoresist pattern is well drawn.
且,(A)含有羧基之樹脂的重量平均分子量會因樹脂骨格而異,但為2,000~150,000,進一步為5,000~100,000之範圍較佳。重量平均分子量為2,000以上時,不剝落性能良好,且曝光後之塗膜的耐濕性良好,並能抑制顯像時的膜減少,並抑制解像度的降低。另一方面,重量平均分子量為150,000以下時,顯像性良好,且儲藏安定性也較優異。重量平均分子量能夠以透膠層析術來測定。 In addition, the weight average molecular weight of the (A) carboxyl group-containing resin varies depending on the resin skeleton, but is preferably in the range of 2,000 to 150,000, and more preferably in the range of 5,000 to 100,000. When the weight-average molecular weight is 2,000 or more, the non-peeling performance is good, and the moisture resistance of the coating film after exposure is good, and it is possible to suppress film reduction during development and to suppress reduction in resolution. On the other hand, when the weight average molecular weight is 150,000 or less, the developability is good and the storage stability is also excellent. The weight average molecular weight can be measured by permeation chromatography.
上述含有羧基之樹脂當中,上述樹脂之合成所使用的多官能環氧樹脂為具有選自雙酚A構造、雙酚F構造、雙二甲苯酚構造、雙酚酚醛構造、雙二甲苯酚構造以及聯苯酚醛構造所成群中的部分構造之多官能環氧樹脂或其氫化化合物時,或者為具有氨基甲酸乙酯構造之含有羧基之樹脂時,以所得之硬化物的低彎曲、折疊耐性之觀 點來看較佳。 Among the carboxyl group-containing resins, the polyfunctional epoxy resin used for the synthesis of the resin has a structure selected from a bisphenol A structure, a bisphenol F structure, a bisxylenol structure, a bisphenol novolac structure, a bisxylenol structure, and In the case of a partially-structured polyfunctional epoxy resin or a hydrogenated compound thereof in a group formed by a biphenol aldehyde structure, or a carboxyl group-containing resin having a urethane structure, the resulting cured product has low bending and folding resistance. View Point of view is better.
且,具有氨基甲酸乙酯構造的含有羧基之樹脂當中,作為具有異氰酸酯基的成分(亦包含二異氰酸酯),使用異氰酸酯基沒有直接鍵結苯環的二異氰酸酯所得之含有羧基之氨基甲酸乙酯樹脂,由於其黃變色較少,對隱蔽性有效,且紫外線吸收較少,故作為鹼顯像性組成物時,具有解像性優異之特徵,故較佳。 In addition, among carboxyl group-containing resins having a urethane structure, as a component having an isocyanate group (including a diisocyanate), a carboxyl group-containing urethane resin is obtained by using a diisocyanate group in which an isocyanate group does not directly bond a benzene ring. Since it has less yellow discoloration, is effective for concealment, and has less ultraviolet absorption, it is preferred as an alkali developable composition because it has excellent resolvability.
(A)含有羧基之樹脂的摻混量以固體分換算,在全組成物中,較佳為5~60質量%,再較佳為10~60質量%,更佳為15~50質量%。5質量%以上時,塗膜強度變得良好。另一方面,為60質量%以下時,組成物的黏性不會變得過高,且塗布性等亦良好。 (A) The compounding amount of the carboxyl group-containing resin is in terms of solid content. In the entire composition, it is preferably 5 to 60% by mass, still more preferably 10 to 60% by mass, and even more preferably 15 to 50% by mass. When it is 5 mass% or more, the coating film strength becomes good. On the other hand, when it is 60% by mass or less, the viscosity of the composition does not become too high, and the coatability and the like are also good.
本發明之感光性樹脂組成物含有(B)官能基數為6個以上的氨基甲酸乙酯(甲基)丙烯酸酯。於此所述之官能基意指丙烯醯基或甲基丙烯醯基。官能基數為6~15較佳。為上述範圍時,能夠使塗膜之折疊性與解像性兩立,且刮痕耐性更優異。 The photosensitive resin composition of the present invention contains (B) a urethane (meth) acrylate having 6 or more functional groups. The functional group described herein means acrylfluorenyl or methacrylfluorenyl. The number of functional groups is preferably 6 to 15. When it is in the said range, the folding property and resolvability of a coating film can be made compatible, and scratch resistance is more excellent.
(B)官能基數為6個以上的氨基甲酸乙酯(甲基)丙烯酸酯的重量平均分子量為1,500~200,000較佳。為上述範圍時,能夠使硬化部的耐顯像性與未硬化部的顯像性兩立,且刮痕耐性更優異。再較佳為1,500~40,000。 (B) The weight average molecular weight of the urethane (meth) acrylate having 6 or more functional groups is preferably 1,500 to 200,000. When it is in the said range, the developability of a hardened part and the developability of an unhardened part can be made to stand, and scratch resistance is more excellent. More preferably, it is 1,500 to 40,000.
作為(B)氨基甲酸乙酯(甲基)丙烯酸酯,能夠 使用根上工業公司製Art Resin UN-3320HA、UN-3320HABA、UN-3320HB、UN-3320HC、UN-3320HS、UN-904、UN-901T、UN-905、UN-952、daicel-allnex公司製EBECRYL220、5129、8301、daicel-allnex公司製KRM8200、8200AE、8452、Sartomer公司製CN968、975、新中村化學工業公司製U-6LPA、U-10HA、U-10PA、UA-1100H、U-15HA、UA-53H、UA-33H等。(B)氨基甲酸乙酯(甲基)丙烯酸酯能夠單獨使用1種或組合2種以上來使用。 As (B) urethane (meth) acrylate, it is possible to Use Art Resin UN-3320HA, UN-3320HABA, UN-3320HB, UN-3320HC, UN-3320HS, UN-904, UN-901T, UN-905, UN-952, Daicel-allnex company made EBECRYL220, 5129, 8301, Daicel-allnex company KRM8200, 8200AE, 8452, Sartomer company CN968, 975, Shin Nakamura Chemical Industry Company U-6LPA, U-10HA, U-10PA, UA-1100H, U-15HA, UA- 53H, UA-33H, etc. (B) A urethane (meth) acrylate can be used individually by 1 type or in combination of 2 or more types.
(B)氨基甲酸乙酯(甲基)丙烯酸酯的摻混量為相對於(A)含有羧基之樹脂100質量份,為10~200質量份較佳。為上述範圍時,能夠保有硬化部之耐顯像性與未硬化部之顯像性的對比,解像性亦較優異。且,光澤性更優異。再較佳為10~150質量份。且,本發明之感光性樹脂組成物除了(B)氨基甲酸乙酯(甲基)丙烯酸酯以外,亦含有在分子中具有1個以上乙烯性不飽和基之化合物(光聚合性單體)。 The blending amount of the (B) urethane (meth) acrylate is preferably 10 to 200 parts by mass relative to 100 parts by mass of the resin having a carboxyl group in (A). In the above range, the contrast between the developability of the hardened portion and the developability of the unhardened portion can be maintained, and the resolution is also excellent. In addition, the gloss is more excellent. More preferably, it is 10 to 150 parts by mass. In addition, the photosensitive resin composition of the present invention contains, in addition to (B) a urethane (meth) acrylate, a compound (photopolymerizable monomer) having one or more ethylenically unsaturated groups in the molecule.
(B)氨基甲酸乙酯(甲基)丙烯酸酯不包含羧基較佳。 (B) The urethane (meth) acrylate does not contain a carboxyl group.
本發明之感光性樹脂組成物含有(C)光聚合起始劑。作為(C)光聚合起始劑,能夠適當地使用選自具有肟酯基之肟酯系光聚合起始劑、烷基乙酮系光聚合起始劑、α-胺苯乙酮系光聚合起始劑、醯基膦氧化物系光聚合起始劑、 二茂鈦系光聚合起始劑所成之群中之1種以上光聚合起始劑。上述肟酯系光聚合起始劑由於以少量添加量即能完成,並能抑制排氣,故在PCT耐性或裂痕抗性上具有效果且較佳。 The photosensitive resin composition of the present invention contains (C) a photopolymerization initiator. As the (C) photopolymerization initiator, an oxime ester-based photopolymerization initiator having an oxime ester group, an alkylacetone-based photopolymerization initiator, and α-aminoacetophenone-based photopolymerization can be appropriately used. Initiator, fluorenylphosphine oxide-based photopolymerization initiator, One or more photopolymerization initiators in the group formed by the titanocene-based photopolymerization initiator. The oxime ester-based photopolymerization initiator can be completed with a small amount of addition, and can suppress exhaust gas, so it is effective and preferable in terms of PCT resistance or crack resistance.
作為肟酯系光聚合起始劑,有舉出作為市售品的BASF Japan公司製之CGI-325,IRGACURE-OXE01,IRGACURE-OXE02,ADEKA公司製N-1919,NCI-831等。且,亦能夠適當地使用在分子內具有2個肟酯基之光聚合起始劑。作為肟酯系光聚合起始劑以具有咔唑構造之化合物特別佳。 Examples of the oxime ester-based photopolymerization initiator include CGI-325, IRGACURE-OXE01, IRGACURE-OXE02, ADEKA N-1919, and NCI-831 manufactured by BASF Japan, which are commercially available products. In addition, a photopolymerization initiator having two oxime ester groups in the molecule can be suitably used. The oxime ester-based photopolymerization initiator is particularly preferably a compound having a carbazole structure.
如此之肟酯系光聚合起始劑的摻混量,設作相對於(A)含有羧基之樹脂100質量份為0.01~10質量份較佳,為0.25~5質量份再較佳。藉由設作0.01~10質量份,能夠得到光硬化性以及解像性優異,密著性或PCT耐性也能提升,且無電解金鍍敷耐性等耐藥品性亦優異之硬化膜。尤其是若在5質量份以下,則能夠抑制在塗膜表面的光吸收變得激烈所造成的深部硬化性之降低。 The blending amount of such an oxime ester-based photopolymerization initiator is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the resin having a carboxyl group (A), and more preferably 0.25 to 5 parts by mass. By setting 0.01 to 10 parts by mass, a cured film having excellent photo-hardening properties and resolving properties, improved adhesion and PCT resistance, and excellent chemical resistance such as electroless gold plating resistance can be obtained. In particular, if it is 5 parts by mass or less, it is possible to suppress a decrease in deep hardenability due to intense light absorption on the surface of the coating film.
作為烷基乙酮系光聚合起始劑之市售品,有舉出BASF Japan公司製IRGACURE-184、DAROCUR-1173、IRGACURE-2959、IRGACURE-127等之α-羥烷基乙酮型。 Examples of commercially available products of the alkyl ethyl ketone-based photopolymerization initiator include α-hydroxyalkyl ethyl ketone types such as IRGACURE-184, DAROCUR-1173, IRGACURE-2959, and IRGACURE-127 manufactured by BASF Japan.
作為α-胺苯乙酮系光聚合起始劑,具體來說有舉出2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉基丙酮-1,2-苄基-2-二甲胺基-1-(4-嗎林基苯基)-丁烷-1-酮、2-(二甲胺基)- 2-[(4-苯甲)甲基]-1-[4-(4-嗎咻基)苯基]-1-丁酮、N,N-二甲基胺苯乙酮等。作為市售品,有舉出BASF Japan公司製之IRGACURE-907、IRGACURE-369、IRGACURE-379等。 Examples of the α-aminoacetophenone-based photopolymerization initiator include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinylacetone-1,2- Benzyl-2-dimethylamino-1- (4-morpholinylphenyl) -butane-1-one, 2- (dimethylamino)- 2-[(4-Benzyl) methyl] -1- [4- (4-morphino) phenyl] -1-butanone, N, N-dimethylamine acetophenone, and the like. Examples of commercially available products include IRGACURE-907, IRGACURE-369, and IRGACURE-379 manufactured by BASF Japan.
作為醯基膦氧化物系光聚合起始劑,具體來說有舉出2,4,6-三甲基苯甲醯基二苯基膦氧化物、雙(2,4,6-三甲基苯甲醯基)-苯基膦氧化物、雙(2,6-二甲氧基苄醯基)-2,4,4-三甲基-戊基膦氧化物等。作為市售品,有舉出BASF公司製之LUCIRIN TPO、BASF Japan公司製之IRGACURE-819等。 Specific examples of the fluorenylphosphine oxide-based photopolymerization initiator include 2,4,6-trimethylbenzylfluorenyldiphenylphosphine oxide and bis (2,4,6-trimethyl Benzamidine) -phenylphosphine oxide, bis (2,6-dimethoxybenzylfluorenyl) -2,4,4-trimethyl-pentylphosphine oxide, and the like. Examples of commercially available products include LUCIRIN TPO manufactured by BASF, and IRGACURE-819 manufactured by BASF Japan.
此等α-胺苯乙酮系光聚合起始劑、醯基膦氧化物系光聚合起始劑的摻混量以相對於(A)含有羧基之樹脂100質量份為0.1~25質量份較佳,為1~20質量份再較佳。藉由為0.1~25質量份,能夠得到光硬化性以及解像性優異,密著性或PCT耐性也提升,且無電解金鍍敷耐性等之耐藥品性亦優異之硬化膜。尤其是,若為25質量份以下,則會得到排氣的降低效果,進一步能夠抑制在塗膜表面的光吸收變得激烈所造成的深部硬化性之降低。 The blending amount of these α-aminoacetophenone-based photopolymerization initiators and fluorenylphosphine oxide-based photopolymerization initiators is 0.1 to 25 parts by mass relative to 100 parts by mass of the resin containing a carboxyl group (A). It is preferably from 1 to 20 parts by mass. When it is 0.1 to 25 parts by mass, a cured film having excellent photohardenability and resolution, improved adhesion and PCT resistance, and excellent chemical resistance such as electroless gold plating resistance can be obtained. In particular, if the content is 25 parts by mass or less, the effect of reducing exhaust gas is obtained, and further, it is possible to suppress a decrease in deep hardenability due to intense light absorption on the surface of the coating film.
且,作為光聚合起始劑,也能夠適當地使用BASF Japan製之IRGACURE-389。IRGACURE-389之較適當的摻混量以相對於上述含有羧基之樹脂100質量份為0.1~20質量份,進而較適合為1~15質量份。 Furthermore, as a photopolymerization initiator, IRGACURE-389 made by BASF Japan can also be used suitably. A more suitable blending amount of IRGACURE-389 is 0.1 to 20 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin, and more preferably 1 to 15 parts by mass.
且,亦能夠適當地使用IRGACURE-784等之二茂鈦系光聚合起始劑。二茂鈦系光聚合起始劑之較適合 的摻混量以相對於含有羧基之樹脂100質量份,為0.01~5質量份,進而較適合的摻混量為0.01~3質量份。 Furthermore, a titanocene-based photopolymerization initiator such as IRGACURE-784 can also be suitably used. A more suitable titanocene-based photopolymerization initiator The blending amount is 0.01 to 5 parts by mass relative to 100 parts by mass of the carboxyl group-containing resin, and a more suitable blending amount is 0.01 to 3 parts by mass.
藉由將此等之光聚合起始劑設在適合的摻混量,能夠得到光硬化性以及解像性優異,密著性或PCT耐性亦提升,且無電解金鍍敷耐性等之耐藥品性亦優異的硬化物。且,為適當的摻混量時,會得到排氣的降低效果,進一步能夠抑制在塗膜表面的光吸收變得激烈所造成的深部硬化性之降低。 By setting these photopolymerization initiators in an appropriate blending amount, it is possible to obtain chemicals that are excellent in photohardening and resolving properties, improve adhesion and PCT resistance, and have electroless gold plating resistance. Hardened material with excellent properties. In addition, when it is an appropriate blending amount, the effect of reducing exhaust gas is obtained, and further, it is possible to suppress a decrease in deep hardenability due to intense light absorption on the surface of the coating film.
上述感光性樹脂組成物除了光聚合起始劑之外,也能夠使用光起始助劑、增感劑。作為能夠適當地使用在感光性樹脂組成物中的光聚合起始劑、光起始助劑以及增感劑,能夠舉例安息香化合物、苯乙酮化合物、菎蔥化合物、噻噸酮化合物、縮酮化合物、二苯基酮化合物、三級胺化合物以及氧葱酮化合物等。 The photosensitive resin composition can use a photoinitiator and a sensitizer in addition to the photopolymerization initiator. Examples of the photopolymerization initiator, photoinitiator, and sensitizer that can be suitably used in the photosensitive resin composition include a benzoin compound, an acetophenone compound, an onion compound, a thioxanthone compound, and a ketal. Compounds, diphenyl ketone compounds, tertiary amine compounds, and allicone compounds.
此等之光聚合起始劑、光起始助劑以及增感劑能夠單獨使用1種或組合2種以上來使用。如此之光聚合起始劑、光起始助劑以及增感劑的總量以相對於(A)含有羧基之樹脂100質量份為35質量份以下較佳。若在35質量份以下,則能夠抑制此等之光吸收所造成的深部硬化性降低。 These photopolymerization initiators, photoinitiators and sensitizers can be used alone or in combination of two or more. The total amount of the photopolymerization initiator, photoinitiator, and sensitizer is preferably 35 parts by mass or less with respect to 100 parts by mass of the resin having a carboxyl group (A). If it is 35 parts by mass or less, it is possible to suppress a decrease in deep hardenability due to such light absorption.
作為(D)氧化鈦,亦可為金紅石型氧化鈦,亦可為銳鈦礦型氧化鈦,但使用金紅石型氧化鈦較佳。同樣為氧化 鈦的銳鈦礦型氧化鈦相較於金紅石型氧化鈦白色度較高,時常被作為白色顏料來使用,但由於銳鈦礦型氧化鈦具有光觸媒活性,故有時尤其是因為由LED所照射的光,而引起感光性樹脂組成物中之樹脂的變色。相對於此,雖然金紅石型氧化鈦的白色度相較於銳鈦礦型略差,但是由於幾乎不具有光活性,故能夠顯著地抑制起因於氧化鈦之光活性的光所造成的樹脂之惡化(黃變色),且對熱也較安定。因此,裝載有LED的印刷配線板之絕緣層中,作為白色顏料使用時,能夠長時間下維持高反射率。 (D) Titanium oxide may be rutile-type titanium oxide or anatase-type titanium oxide, but it is preferable to use rutile-type titanium oxide. Same oxidation Compared with rutile titanium oxide, titanium anatase titanium oxide has a higher whiteness and is often used as a white pigment. However, because anatase titanium oxide has photocatalytic activity, it is sometimes caused especially by LEDs. The irradiated light causes discoloration of the resin in the photosensitive resin composition. On the other hand, although the whiteness of rutile-type titanium oxide is slightly inferior to that of anatase, it has almost no photoactivity, so it can significantly suppress the resin caused by the photoactive light of titanium oxide. It deteriorates (yellow discoloration) and is more stable to heat. Therefore, when used as a white pigment in an insulating layer of a printed wiring board on which LEDs are mounted, high reflectance can be maintained for a long time.
作為金紅石型氧化鈦,能夠使用周知者。金紅石型氧化鈦之製造法中,具有硫酸法與氯原子法2種類,且本發明中能夠適當地使用任一者製造法所製造者。於此,硫酸法是意指將鈦鐵礦礦石或鈦渣作為原料,將此溶解於濃硫酸中,並將鐵部分作為硫酸鐵分離,再將溶液水解,藉此得到氫氧化物之沉澱物,將此以高溫進行燒成,取出金紅石型氧化鈦之製法。另一方面,氯原子法是意指將合成金紅石或天然金紅石作為原料,將此以約1000℃之高溫與氯氣與碳進行反應,合成四氯化鈦,再將此氧化並取出金紅石型氧化鈦之製法。其中,氯原子法所製造出的金紅石型氧化鈦尤其是熱所造成的樹脂劣化(黃變色)之抑制效果較顯著,更適當地使用在本發明中。 As the rutile titanium oxide, a known one can be used. The rutile-type titanium oxide production method includes two types, a sulfuric acid method and a chlorine atom method, and any one of the production methods can be appropriately used in the present invention. Here, the sulfuric acid method means taking ilmenite ore or titanium slag as a raw material, dissolving this in concentrated sulfuric acid, separating the iron portion as iron sulfate, and then hydrolyzing the solution to obtain a hydroxide precipitate. This method is a method of firing at high temperature to take out a rutile titanium oxide. On the other hand, the chlorine atom method means that synthetic rutile or natural rutile is used as a raw material, and this is reacted with chlorine gas and carbon at a high temperature of about 1000 ° C to synthesize titanium tetrachloride, and then oxidize and remove the rutile. Production method of titanium oxide. Among them, the rutile-type titanium oxide produced by the chlorine atom method is particularly effective in suppressing resin degradation (yellow discoloration) caused by heat, and is more suitably used in the present invention.
在此等之氧化鈦中,可使用表面經含水氧化鋁或氫氧化鋁處理之氧化鈦,但以組成物中的分散性、保存安定性、難燃性之觀點來看,特別佳。 Among these titanium oxides, titanium oxide having a surface treated with hydrous alumina or aluminum hydroxide can be used, but it is particularly preferable from the viewpoints of dispersibility, storage stability, and flame retardancy in the composition.
且,由本發明之感光性樹脂組成物所形成之硬化物,Y值為65以上較佳,為70以上再較佳。 In addition, the cured product formed from the photosensitive resin composition of the present invention preferably has a Y value of 65 or more, and more preferably 70 or more.
(D)氧化鈦的摻混量以相對於(A)含有羧基之樹脂100質量份,較佳為30~300質量份,再較佳為50~250質量份。(D)氧化鈦可單獨使用1種或組合2種以上來使用。且,在不損及本發明效果之範圍內,亦可含有氧化鈦以外的其他著色劑。 The blending amount of (D) titanium oxide is preferably 30 to 300 parts by mass, and more preferably 50 to 250 parts by mass with respect to 100 parts by mass of the resin containing a carboxyl group (A). (D) Titanium oxide can be used individually by 1 type or in combination of 2 or more types. In addition, as long as the effect of the present invention is not impaired, colorants other than titanium oxide may be contained.
(D)氧化鈦亦可為以二氧化矽或氧化鋁表面處理者。 (D) Titanium oxide may be a surface treated with silicon dioxide or aluminum oxide.
以二氧化矽表面處理的氧化鈦能夠抑制對光的惡化。以氧化鋁表面處理的氧化鈦能夠進一步提升硬化物的反射率。以二氧化矽或氧化鋁表面處理的氧化鈦可使用銳鈦礦型亦可使用金紅石型,但為金紅石型較佳。且,金紅石型氧化鈦之中,以氯原子法所製造者可進一步抑制樹脂的惡化,故特別佳。 Titanium oxide surface-treated with silicon dioxide can suppress deterioration of light. Titanium oxide surface-treated with alumina can further increase the reflectivity of the hardened material. Titanium oxide surface-treated with silicon dioxide or alumina can be either anatase or rutile, but it is preferably rutile. In addition, among the rutile titanium oxides, those produced by the chlorine atom method can further suppress deterioration of the resin, which is particularly preferable.
作為以二氧化矽或氧化鋁表面處理之氧化鈦,能夠使用Tipaque R-930、Tipaque R-630、Tipaque R-680、Tipaque R-670、Tipaque CR-50、Tipaque CR-57、Tipaque CR-97、Tipaque CR-60、Tipaque CR-63、Tipaque CR-67、Tipaque CR-58、Tipaque UT771、Tipaque R-820、Tipaque R-830、Tipaque R-550、Tipaque R-780、Tipaque R-780-2、Tipaque R-850、Tipaque R-855、Tipaque CR-80、Tipaque CR-90、Tipaque CR-90、Tipaque CR-90-2、Tipaque CR-93、Tipaque CR-95、Tipaque CR- 953、Tipaque CR-63、Tipaque CR-85(石原產業公司製)、Taipyua R-100、Taipyua R-101、Taipyua R-102、Taipyua R-103、Taipyua R-104、Taipyua R-105、Taipyua R-108、Taipyua R-900、Taipyua R-902、Taipyua R-960、Taipyua R-706、Taipyua R-931(Du Pont公司製)、TITON R-25、TITON R-21、TITON R-32、TITON R-7E、TITON R-5N、TITON R-61N、TITON R-62N、TITON R-42、TITON R-45M、TITON R-44、TITON R-49S、TITON GTR-100、TITON GTR-300、TITON D-918、TITON TCR-29、TITON TCR-52、TITON FTR-700(堺化學工業公司製)、TITANIX JR-300、TITANIX JR-403、TITANIX JR-405、TITANIX JR-600A、TITANIX JR-600E、TITANIX JR-602、TITANIX JR-602S、TITANIX JR-603、TITANIX JR-805(Tayca公司製)等。 As titanium oxide with silicon dioxide or alumina surface treatment, Tipaque R-930, Tipaque R-630, Tipaque R-680, Tipaque R-670, Tipaque CR-50, Tipaque CR-57, Tipaque CR-97 can be used. , Tipaque CR-60, Tipaque CR-63, Tipaque CR-67, Tipaque CR-58, Tipaque UT771, Tipaque R-820, Tipaque R-830, Tipaque R-550, Tipaque R-780, Tipaque R-780-2 , Tipaque R-850, Tipaque R-855, Tipaque CR-80, Tipaque CR-90, Tipaque CR-90, Tipaque CR-90-2, Tipaque CR-93, Tipaque CR-95, Tipaque CR- 953, Tipaque CR-63, Tipaque CR-85 (manufactured by Ishihara Industries), Taipuya R-100, Taipuya R-101, Taipuya R-102, Taipuya R-103, Taipuya R-104, Taipuya R-105, Taipuya R -108, Taipuya R-900, Taipuya R-902, Taipuya R-960, Taipuya R-706, Taipuya R-931 (manufactured by Du Pont), TITON R-25, TITON R-21, TITON R-32, TITON R-7E, TITON R-5N, TITON R-61N, TITON R-62N, TITON R-42, TITON R-45M, TITON R-44, TITON R-49S, TITON GTR-100, TITON GTR-300, TITON D-918, TITON TCR-29, TITON TCR-52, TITON FTR-700 (manufactured by Sakai Chemical Industry Co., Ltd.), TITANIX JR-300, TITANIX JR-403, TITANIX JR-405, TITANIX JR-600A, TITANIX JR-600E , TITANIX JR-602, TITANIX JR-602S, TITANIX JR-603, TITANIX JR-805 (made by Tayca) and so on.
且,作為銳鈦礦型氧化鈦,有舉出Tipaque A-220(石原產業公司製)、TITANIX JA-4(Tayca公司製)等。 Examples of the anatase-type titanium oxide include Tipaque A-220 (manufactured by Ishihara Industries Co., Ltd.), TITANIX JA-4 (manufactured by Tayca Corporation), and the like.
以氧化鋁表面處理之氧化鈦,在以氧化鋁表面處理之後能夠進一步進行其他的表面處理。尤其是,在以氧化鋁表面處理之後,藉由以氧化鋯進一步進行表面處理,能夠更加提升反射率。 The titanium oxide surface-treated with alumina can be further subjected to other surface treatments after being surface-treated with alumina. In particular, after surface treatment with alumina, further surface treatment with zirconia can further increase the reflectance.
在上述氧化鈦中,作為以氧化鋁表面處理之後再以氧化鋯表面處理之氧化鈦,有舉出Tipaque CR-57、Tipaque CR-97、Tipaque CR-67(石原產業公司製)、R-61N、GTR-100、GTR-300(堺化學工業公司製)、TITANIX JR- 603(Tayca公司製)。 Among the above-mentioned titanium oxides, as the titanium oxide treated with alumina surface and then with zirconia surface treatment, there are Tipaque CR-57, Tipaque CR-97, Tipaque CR-67 (made by Ishihara Industry Co., Ltd.), and R-61N , GTR-100, GTR-300 (manufactured by Sakai Chemical Industry Co., Ltd.), TITANIX JR- 603 (manufactured by Tayca).
本發明之感光性樹脂組成物,以提升所得之硬化物的難燃性為目的,含有慣用周知的難燃劑較佳。以對於環境之觀點來看,以不包含鹵素之難燃劑較佳。作為難燃劑,亦可摻混例如含有磷之化合物或賦予樹脂組成物難燃性之無機填料的氫氧化鋁、氫氧化鎂、水滑石類以及水鋁石等。難燃劑之中,以含有磷之化合物與金屬氫氧化物較佳。難燃劑能夠單獨使用1種或組合2種以上來使用。 The photosensitive resin composition of the present invention preferably contains a conventionally known flame retardant for the purpose of improving the flame retardancy of the obtained cured product. From an environmental point of view, a flame retardant containing no halogen is preferred. As the flame retardant, for example, aluminum hydroxide, magnesium hydroxide, hydrotalcite, gibbsite, and the like may be blended with a compound containing phosphorus or an inorganic filler that imparts flame resistance to the resin composition. Among the flame retardants, phosphorus-containing compounds and metal hydroxides are preferred. A flame retardant can be used individually by 1 type or in combination of 2 or more types.
作為含有磷之化合物,有舉出周知作為有機磷系難燃劑者。如此之有機磷系難燃劑中,作為較適合者,有舉出磷酸酯以及縮合磷酸酯、含有磷元素之(甲基)丙烯酸酯、具有苯酚性羥基之含有磷之化合物、環狀偶磷氮化合物、磷氮環寡聚物、膦酸金屬鹽、下述一般式(I)所表示之化合物。 Examples of compounds containing phosphorus include those known as organophosphorus flame retardants. Among such organic phosphorus-based flame retardants, suitable examples include phosphate esters and condensed phosphate esters, (meth) acrylates containing phosphorus elements, phosphorus-containing compounds having phenolic hydroxyl groups, and cyclic phosphorous A nitrogen compound, a phosphorus nitrogen ring oligomer, a phosphonic acid metal salt, and a compound represented by the following general formula (I).
上述一般式(I)中,R5、R6為氫原子或碳原子數1~4之烷基較佳,R7為亦可經氫原子、氰基所取代之碳原子數1~4之烷基、2,5-二羥苯基或3,5-二-t-丁基-4-羥苯基較佳,但不限定於此。 In the above general formula (I), R 5 and R 6 are preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 7 is an alkyl group having 1 to 4 carbon atoms which may be substituted by a hydrogen atom or a cyano group. Alkyl, 2,5-dihydroxyphenyl, or 3,5-di-t-butyl-4-hydroxyphenyl is preferred, but is not limited thereto.
作為上述一般式(I)所表示之含有磷之化合物的市售品,有HCA、SANKO-220、M-ESTER、HCA-HQ(皆為三光公司的商品名)等。 Commercial products of the phosphorus-containing compound represented by the general formula (I) include HCA, SANKO-220, M-ESTER, HCA-HQ (all are trade names of Sanko Corporation), and the like.
含有磷元素之(甲基)丙烯酸酯為具有磷元素,且為在分子中具有複數(甲基)丙烯醯基之化合物較佳,具體來說有舉出上述一般式(I)中之R5與R6為氫原子,R7為(甲基)丙烯酸酯衍生物之化合物。一般來說,能夠藉由9,10-二氫-9-氧雜-10-膦菲(phosphaphenanthrene)-10-氧化物與周知慣用的多官能(甲基)丙烯酸酯單體之麥克加成反應來合成。 The (meth) acrylate containing a phosphorus element is preferably a compound having a phosphorus element and a plurality of (meth) acrylfluorenyl groups in the molecule, and specifically, R 5 in the general formula (I) is mentioned above. Compounds in which R 6 is a hydrogen atom and R 7 is a (meth) acrylate derivative. In general, it is possible to perform a Mack addition reaction of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide with a well-known and commonly used multifunctional (meth) acrylate monomer. To synthesize.
作為上述(甲基)丙烯酸酯單體,有舉出乙烯二醇、甲氧基四乙烯二醇、聚乙烯二醇、丙二醇等之乙二醇的二丙烯酸酯類;己二醇、三羥甲丙烷、季戊四醇、二季戊四醇、參-羥乙基異氰酯等之多價醇或此等之氧乙烷加成物、氧化丙烯加成物或己內酯加成物等之多價丙烯酸酯類;苯氧基丙烯酸酯、雙酚A二丙烯酸酯以及此等之苯酚類的氧乙烷加成物或氧化丙烯加成物等之多價丙烯酸酯類;以及上述聚醇類之氨基甲酸乙酯丙烯酸酯類、丙三醇二氧化丙烯醚、丙三醇三環氧丙基醚、三羥甲丙烷三環氧 丙基醚、三縮水甘油基異三聚氰酸酯等之環氧丙基醚的多價丙烯酸酯類;以及三聚氰胺丙烯酸酯、以及對應於上述丙烯酸酯之各丙烯酸甲酯類中至少任1種等。 Examples of the (meth) acrylate monomer include diacrylates of ethylene glycol such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; hexanediol and trimethylol Polyvalent alcohols such as propane, pentaerythritol, dipentaerythritol, and p-hydroxyethyl isocyanate, or polyoxyacrylate adducts, propylene oxide adducts, or caprolactone adducts, etc. ; Polyvalent acrylates such as phenoxy acrylate, bisphenol A diacrylate and phenols such as oxyethane adducts or propylene oxide adducts; and urethanes of the above-mentioned polyols Acrylates, glycerol propylene oxide ether, glycerol triglycidyl ether, trimethylolpropane triepoxide Polyvalent acrylates of epoxypropyl ethers such as propyl ether, triglycidyl isotricyanate, and melamine acrylate, and at least one of methyl acrylates corresponding to the above acrylates Wait.
具有苯酚性羥基之含有磷之化合物,其疏水性,耐熱性較高,且無水解所造成的電氣特性之降低,焊料耐熱性也較高。且,作為較適當的組合,熱硬化性樹脂中使用環氧樹脂時,會與環氧基反應,且會被系統所吸收,故能夠得到在硬化後不會有溢出之優點。具有苯酚性羥基之含有磷之化合物中,作為較佳者,有舉出在上述一般式(I)中,R7為經羥基取代之苯基者。作為市售品,有三光公司製HCA-HQ等。 Phosphorus-containing phosphorus-containing compounds having phenolic hydroxyl groups have high hydrophobicity and heat resistance, and there is no reduction in electrical characteristics caused by hydrolysis, and solder heat resistance is also high. In addition, as a more suitable combination, when an epoxy resin is used in a thermosetting resin, it reacts with an epoxy group and is absorbed by the system. Therefore, it has the advantage that there is no overflow after curing. Among the phosphorus-containing compounds having a phenolic hydroxyl group, preferred examples include those in which R 7 is a phenyl group substituted with a hydroxyl group in the general formula (I). Examples of commercially available products include HCA-HQ manufactured by Sanko.
寡聚物或聚合物之含有磷之化合物,因烷鏈之影響所造成的折疊性之降低較少,且由於分子量較大,故能夠得到無硬化後之溢出之優點。作為市售品,有三光公司製M-Ester-HP、東洋紡公司製的含有磷之Byron337等。 The oligomer or polymer containing a phosphorus compound has less reduction in foldability due to the influence of an alkane chain, and because of its large molecular weight, it can obtain the advantage of no overflow after hardening. As commercially available products, there are M-Ester-HP manufactured by Sanko, and Byron337 containing phosphorus by Toyobo.
作為磷氮環寡聚物,以苯氧基磷氮環化合物為有效,雖有取代或無取代之苯氧基磷氮環寡聚物或三聚物、四聚物、五聚物之環狀物,且有為液狀或固體粉末者,但能夠適當地使用任一者。作為市售品,有伏見製藥所公司製FP-100、FP-300、FP-390等。其中,經烷基或者羥基或氰基等之極性基取代的苯氧基磷氮環寡聚物,對含有羧基之樹脂之溶解性較高,即時多量添加也不會有再結晶等不良狀況,故較佳。 As a phosphorus-nitrogen ring oligomer, a phenoxy phosphorus-nitrogen ring compound is effective, although substituted or unsubstituted phenoxy phosphorus-nitrogen ring oligomers or cyclic rings of trimers, tetramers, and pentamers And there are liquid or solid powders, but any of them can be used as appropriate. As commercially available products, there are FP-100, FP-300, and FP-390 manufactured by Fushimi Pharmaceutical Co., Ltd. Among them, phenoxy phosphorus nitrogen ring oligomers substituted with polar groups such as alkyl groups, hydroxyl groups or cyano groups have high solubility in carboxyl group-containing resins, and even when added in large amounts, there will be no adverse conditions such as recrystallization. It is better.
且,作為其他磷氮環寡聚物,為下述一般式(II)所表示之含有磷元素之二羧酸以及其酸酐中至少任1種與丙烯酸酯化合物反應所得,且在分子內含有1個以上(甲基)丙烯酸酯之化合物。 In addition, as another phosphorus-nitrogen ring oligomer, a phosphorus acid-containing dicarboxylic acid represented by the following general formula (II) and an anhydride thereof are obtained by reacting at least one kind with an acrylate compound, and contains 1 in the molecule. More than (meth) acrylate compounds.
作為上述一般式(II)中之R8、R9所表示之碳原子數1~6的烴基,有舉例如碳原子數1~6之烷基、碳原子數1~6之烯基、環烷基、苯基。作為碳原子數1~6之烷基,有舉出甲基、乙基、丙基、異丙基、丁基、第二丁基、第三丁基、異丁基、戊基、異戊基、第三戊基、己基等,作為碳原子數1~6之烯基,有舉出乙烯基、丙烯基、3-丁烯基、異丁烯基、4-戊烯基、5-己烯基等。碳原子數1~6之烴基亦可為經分支以及取代之任一種。 Examples of the hydrocarbon group having 1 to 6 carbon atoms represented by R 8 and R 9 in the general formula (II) include an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, and a ring. Alkyl, phenyl. Examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, second butyl, third butyl, isobutyl, pentyl, and isopentyl , Third pentyl, hexyl, etc. Examples of the alkenyl group having 1 to 6 carbon atoms include vinyl, propenyl, 3-butenyl, isobutenyl, 4-pentenyl, 5-hexenyl, etc. . The hydrocarbon group having 1 to 6 carbon atoms may be either branched or substituted.
作為上述含有磷元素之二羧酸或其酸酐之例,有舉出9,10-二氫-9-氧雜-10-膦菲(phosphaphenanthrene)-10-氧化物與伊康酸反應所得之化 合物以及其酸酐等。 Examples of the phosphorus-containing dicarboxylic acid or its anhydride include a reaction obtained by reacting 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide with itaconic acid. Compounds and their anhydrides.
作為上述丙烯酸酯化合物,以具有與上述二羧酸或其酸酐之羧基或羧酸酐反應的官能基之丙烯酸酯化合物較佳。能夠藉由相關之反應來附加丙烯酸酯殘基。如此之丙烯酸酯化合物亦可為分子內含有1個(甲基)丙烯酸酯基之單官能丙烯酸酯,亦可為分子內含有2個以上(甲基)丙烯酸酯基之多官能丙烯酸酯。作為上述官能基,有舉出環氧基、羥基、胺基等。作為具有環氧基之丙烯酸酯化合物,有舉出環氧丙基(甲基)丙烯酸酯、2-甲基-2,3-環氧丙基(甲基)丙烯酸酯等。作為具有羥基之丙烯酸酯化合物,有舉出2-羥乙基丙烯酸酯、2-羥丙基丙烯酸酯等。作為具有胺基之丙烯酸酯化合物,有舉出二乙基胺乙基丙烯酸酯等。上述官能基之中,以環氧基、羥基再較佳。 The acrylate compound is preferably an acrylate compound having a functional group that reacts with the carboxyl group or carboxylic anhydride of the dicarboxylic acid or its anhydride. Acrylate residues can be added by related reactions. Such an acrylate compound may be a monofunctional acrylate containing one (meth) acrylate group in the molecule, or a polyfunctional acrylate containing two or more (meth) acrylate groups in the molecule. Examples of the functional group include an epoxy group, a hydroxyl group, and an amine group. Examples of the acrylate compound having an epoxy group include glycidyl (meth) acrylate, 2-methyl-2,3-glycidyl (meth) acrylate, and the like. Examples of the acrylate compound having a hydroxyl group include 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate. Examples of the acrylate compound having an amino group include diethylamine ethyl acrylate. Among the above functional groups, an epoxy group and a hydroxyl group are more preferred.
以上述官能基附加之反應方法能夠使用以往習知的反應方法。 As the reaction method in which the functional group is added, a conventionally known reaction method can be used.
作為上述磷氮環寡聚物之例,有舉出如上述例所合成之一般式(II)的含有磷元素之二羧酸與環氧丙基丙烯酸甲酯反應後所得之1或2官能之磷氮環寡聚物、或一般式(II)的含有磷元素之二羧酸與羥基(甲基)丙烯酸酯以及因應必要與二乙醇反應後所得之2官能之磷氮環寡聚物等。 Examples of the phosphorus-nitrogen ring oligomers include the 1- or 2-functional compounds obtained by reacting the phosphorus-containing dicarboxylic acid of the general formula (II) synthesized with the above-mentioned example and glycidyl methacrylate. Phosphorus-nitrogen ring oligomer, or a difunctional phosphorus-nitrogen ring oligomer obtained by reacting diethanol with a dicarboxylic acid and a hydroxy (meth) acrylate of general formula (II) and diethanol if necessary.
相對於上述一般式(II)所表示之含有磷元素之二羧酸或其酸酐,上述丙烯酸酯化合物之添加量並無特別限定,但調整至上述磷氮環寡聚物的磷濃度成為2~7%之 範圍內,來作為丙烯酸酯化合物較佳。 The addition amount of the acrylate compound is not particularly limited with respect to the dicarboxylic acid containing a phosphorus element represented by the general formula (II) or an anhydride thereof, but the phosphorus concentration of the phosphorus-nitrogen ring oligomer is adjusted to 2 to 7% Within the range, it is preferable as the acrylate compound.
藉由使用上述一般式(II)所表示之含有磷元素之二羧酸或其酸酐,能夠容易地得到在兩末端有丙烯酸酯化之磷氮環寡聚物。使用如此所得之末端丙烯酸酯化之磷氮環寡聚物,能夠得到一種感光性樹脂組成物,該感光性樹脂組成物能夠得到可撓性、低彎曲性優異,且在熱壓時不會發生溢出之難燃性被膜。 By using a phosphorus-containing dicarboxylic acid represented by the general formula (II) or an anhydride thereof, a phosphorus-nitrogen ring oligomer having acrylates at both ends can be easily obtained. By using the terminally acrylated phosphorus-nitrogen ring oligomer obtained in this manner, a photosensitive resin composition can be obtained. The photosensitive resin composition is excellent in flexibility and low flexibility, and does not occur during hot pressing. Spilled flame retardant coating.
上述磷氮環寡聚物為2官能之含有磷元素之丙烯酸酯,以可撓性與低彎曲性之觀點來看較佳。磷氮環寡聚物為2官能時,耐熱性變得良好,也能夠抑制可撓性的降低。 The phosphorus-nitrogen ring oligomer is a bifunctional phosphorus element-containing acrylate, and is preferred from the viewpoints of flexibility and low flexibility. When the phosphorus-nitrogen ring oligomer is difunctional, heat resistance becomes good, and reduction in flexibility can also be suppressed.
且,上述磷氮環寡聚物亦可單獨使用1種類,亦可併用2種類以上。 Moreover, the said phosphorus-nitrogen ring oligomer may be used individually by 1 type, and may use 2 or more types together.
且,藉由使用膦酸金屬鹽,能夠不損及硬化被膜的柔軟性並提升難燃性。藉由使用如此之耐熱性優異之膦酸金屬鹽,能夠抑制實裝時在熱壓力下難燃劑的溢出。 In addition, by using a metal phosphonic acid salt, it is possible to improve the flame retardancy without impairing the flexibility of the cured film. By using such a phosphonic acid metal salt excellent in heat resistance, it is possible to suppress the overflow of the flame retardant under thermal pressure during mounting.
作為構成膦酸金屬鹽之膦酸的具體例,有舉出膦酸、二甲基膦酸、乙基甲基膦酸、二乙基膦酸、甲基-n-丙基膦酸、甲烷二(甲基膦酸)、苯-1,4-(二甲基膦酸)、苯甲膦酸、苯膦酸、二苯膦酸以及此等之混合物。 Specific examples of the phosphonic acid constituting the metal phosphonic acid include phosphonic acid, dimethylphosphonic acid, ethylmethylphosphonic acid, diethylphosphonic acid, methyl-n-propylphosphonic acid, and methanediphosphonic acid. (Methylphosphonic acid), benzene-1,4- (dimethylphosphonic acid), benzylphosphonic acid, phenylphosphonic acid, diphenylphosphonic acid, and mixtures thereof.
作為構成膦酸鹽之金屬成分,有例如鈣、鎂、鋁、鋅、鉍、錳、鈉、鉀。較佳為鈣、鎂、鋁、鋅。 Examples of the metal component constituting the phosphonate include calcium, magnesium, aluminum, zinc, bismuth, manganese, sodium, and potassium. Preferred are calcium, magnesium, aluminum, and zinc.
作為膦酸金屬鹽之市售品,有舉出Clariant 公司製之EXOLIT OP 930、EXOLIT OP 935等。 As a commercially available product of a phosphonic acid metal salt, Clariant is mentioned. Company-made EXOLIT OP 930, EXOLIT OP 935, etc.
含有磷之化合物亦可單獨使用1種,亦可併用2種以上。含有磷之化合物的摻混量為相對於上述(A)含有羧基之樹脂100質量份,為5~150質量份,較佳為10~100質量份。為150質量份以下時,所得之硬化被膜的折疊特性等變得良好。 The phosphorus-containing compound may be used alone or in combination of two or more. The compounding amount of the phosphorus-containing compound is 5 to 150 parts by mass, and preferably 10 to 100 parts by mass with respect to 100 parts by mass of the resin having a carboxyl group (A). When it is 150 parts by mass or less, the folding characteristics and the like of the obtained cured film become good.
作為金屬氫氧化物,能夠使用氫氧化鋁、氫氧化鎂、氫氧化鈣、氫氧化鋇、氫氧化鍶等之能夠藉由加熱分解來發揮難燃性者。其中,能夠特別適當地使用氫氧化鋁,氫氧化鎂。 As the metal hydroxide, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, strontium hydroxide, or the like that can exhibit flame resistance by thermal decomposition can be used. Among them, aluminum hydroxide and magnesium hydroxide can be particularly suitably used.
氫氧化鋁亦可為表面未處理者,亦可使用經末端具有乙烯基或環氧基之矽烷偶合劑、十八烷酸、油酸、磷酸酯等進行表面處理者等。作為氫氧化鋁之市售品,有舉出昭和電工公司製之Higilite H-42、H-42M、H-42S、H-42T、H-42ST-V、H-42ST-E、H-42I、H-43、H-43M、H-43S、日本輕金屬公司製之B1403、B1403ST、B1403T等。 The aluminum hydroxide may be an untreated surface, and a surface treatment such as a silane coupling agent having a vinyl group or an epoxy group at its terminal, octadecanoic acid, oleic acid, or a phosphate ester may also be used. As commercially available products of aluminum hydroxide, there are Higilite H-42, H-42M, H-42S, H-42T, H-42ST-V, H-42ST-E, H-42I, manufactured by Showa Denko Corporation. H-43, H-43M, H-43S, B1403, B1403ST, B1403T, etc. made by Japan Light Metal Corporation.
作為氫氧化鎂,亦可為天然物,亦可為合成物,且,亦可為表面未處理者,亦可使用經末端具有乙烯基或環氧基之矽烷偶合劑、十八烷酸、油酸、磷酸酯等進行表面處理者等。作為氫氧化鎂之市售品,有舉出協和化學公司製KISUMA 5A、KISUMA 5B、KISUMA 5E、KISUMA 5J、KISUMA 5P、KISUMA 5L、Albemarle公司製MagnifinH5、MagnifinH7、MagnifinH10等。 Magnesium hydroxide may be a natural product or a synthetic product, and may also be an untreated surface, and a silane coupling agent having a vinyl group or an epoxy group at its terminal, octadecanoic acid, or oil may also be used. Surface treatments such as acids and phosphates. Examples of commercially available products of magnesium hydroxide include KISUMA 5A, KISUMA 5B, KISUMA 5E, KISUMA 5J, KISUMA 5P, KISUMA 5L, and MagnifinH5, MagnifinH7, and MagnifinH10 manufactured by Albemarle.
賦予氫氧化鋁、氫氧化鎂等之難燃性之無機填料的摻混量相對於上述(A)含有羧基之樹脂100質量份,較佳為500質量份以下,再較佳為0.1~300質量份,特別佳為0.1~150質量份。填料的摻混量為500質量份以下時,感光性樹脂組成物的黏度不會過高,印刷性良好,且硬化物難以變脆。 The blending amount of the inorganic filler that imparts flame retardancy such as aluminum hydroxide, magnesium hydroxide, etc. is preferably 500 parts by mass or less, and still more preferably 0.1 to 300 parts by mass relative to 100 parts by mass of the (A) carboxyl group-containing resin. Parts, particularly preferably 0.1 to 150 parts by mass. When the blending amount of the filler is 500 parts by mass or less, the viscosity of the photosensitive resin composition is not excessively high, the printability is good, and the cured product is difficult to become brittle.
賦予難燃性之無機填料的平均粒徑(d50)為30μm以下較佳,為15μm以下再較佳。藉由將平均粒徑設在30μm以下,能夠將磨擦痕跡變得更難以發生。作為平均粒徑(d50)的下限值,例如為0.05μm以上。平均粒徑(d50)能夠藉由雷射繞射/散射法來測定。 The average particle diameter (d50) of the inorganic filler imparting flame resistance is preferably 30 μm or less, and even more preferably 15 μm or less. By setting the average particle diameter to 30 μm or less, it is possible to make friction marks more difficult to occur. The lower limit value of the average particle diameter (d50) is, for example, 0.05 μm or more. The average particle diameter (d50) can be measured by a laser diffraction / scattering method.
本發明之感光性樹脂組成物中摻混熱硬化成分較佳。藉由添加熱硬化成分,能夠期待耐熱性會提升。作為熱硬化成分,能夠使用習知者之任一者。例如能夠使用三聚氰胺樹脂、苯胍胺樹脂、三聚氰胺衍生物、苯胍胺衍生物等之胺基樹脂、異氰酸酯化合物、嵌段異氰酸酯化合物、環狀碳酸鹽化合物、多官能環氧化合物、多官能環氧丙烷化合物、環氧硫化物樹脂、雙馬來醯亞胺、碳二醯亞胺樹脂等之習知的熱硬化成分。特別佳為在分子中具有複數個環狀***基或環狀乙硫醚基(以下略稱作環狀(硫)***基)之熱硬化成分。熱硬化成分能夠單獨使用1種或組合2種以上來使用。 The photosensitive resin composition of the present invention is preferably blended with a thermosetting component. By adding a thermosetting component, heat resistance can be expected to improve. As the thermosetting component, any one of known ones can be used. For example, amine resins such as melamine resins, benzoguanamine resins, melamine derivatives, benzoguanamine derivatives, isocyanate compounds, block isocyanate compounds, cyclic carbonate compounds, polyfunctional epoxy compounds, and polyfunctional epoxy resins can be used. Conventional thermosetting components such as propane compounds, epoxy sulfide resins, bismaleimide, and carbodiimide resins. Particularly preferred is a thermosetting component having a plurality of cyclic ether groups or cyclic ethyl sulfide groups (hereinafter abbreviated as cyclic (thio) ether groups) in the molecule. A thermosetting component can be used individually by 1 type or in combination of 2 or more types.
上述之分子中具有複數個環狀(硫)***基之熱硬化成分為分子中具有複數個3、4或5員環之環狀(硫)***基之化合物,有舉例如在分子內具有複數個環氧基之化合物,亦即多官能環氧化合物、分子內具有複數個環氧丙烷基之化合物,亦即多官能環氧丙烷化合物、分子內具有複數個乙硫醚基之化合物,亦即環氧硫化物樹脂等。 The heat-hardening component having a plurality of cyclic (thio) ether groups in the above-mentioned molecule is a compound having a plurality of cyclic (thio) ether groups having 3, 4 or 5 members in the molecule. Epoxy compounds, that is, polyfunctional epoxy compounds, compounds having a plurality of propylene oxide groups in the molecule, that is, polyfunctional propylene oxide compounds, compounds having a plurality of ethyl sulfide groups in the molecule, that is, Epoxy sulfide resin, etc.
作為多官能環氧化合物,有舉出環氧化植物油;雙酚A型環氧樹脂;氫醌型環氧樹脂;雙酚型環氧樹脂;乙硫醚型環氧樹脂;溴化環氧樹脂;酚醛型環氧樹脂;雙苯酚酚醛型環氧樹脂;雙酚F型環氧樹脂;氫化雙酚A型環氧樹脂;環氧丙基胺型環氧樹脂;乙內醯脲型環氧樹脂;脂環式環氧樹脂;三羥基苯基甲烷型環氧樹脂;雙二甲苯酚型或雙苯酚型環氧樹脂或此等之混合物;雙酚S型環氧樹脂;雙酚A酚醛型環氧樹脂;四乙苯型環氧樹脂;複素環式環氧樹脂;二環氧丙基鄰苯二甲酸酯樹脂;四縮水甘油基二甲苯醯基乙烷樹脂;含有萘基之環氧樹脂;具有倍環戊二烯骨架之環氧樹脂;環氧丙基丙烯酸甲酯共聚合系環氧樹脂;環己基馬來醯亞胺與環氧丙基丙烯酸甲酯之共聚合環氧樹脂;環氧改質之聚丁二烯橡膠衍生物;CTBN改質環氧樹脂等,但不限定於此等。此等之環氧樹脂能夠單獨使用1種或組合2種以上來使用。此等之中,尤其是酚醛型環氧樹脂、雙酚型環氧樹脂、雙二甲苯酚型環氧樹脂、雙苯酚型環氧樹脂、雙苯酚酚醛型環氧樹脂、萘型環氧樹脂或此等之混合物較佳。 Examples of the polyfunctional epoxy compound include epoxidized vegetable oil; bisphenol A epoxy resin; hydroquinone epoxy resin; bisphenol epoxy resin; ethyl sulfide epoxy resin; brominated epoxy resin; Phenolic epoxy resin; bisphenol novolac epoxy resin; bisphenol F epoxy resin; hydrogenated bisphenol A epoxy resin; epoxypropylamine epoxy resin; hydantoin epoxy resin; Alicyclic epoxy resins; trihydroxyphenylmethane epoxy resins; bisxylenol or bisphenol epoxy resins or mixtures thereof; bisphenol S epoxy resins; bisphenol A phenolic epoxy resins Resin; Tetraethylbenzene type epoxy resin; Compound cyclic epoxy resin; Diglycidyl phthalate resin; Tetraglycidyl xylenyl ethane resin; Naphthyl-containing epoxy resin; Epoxy resin with sesquicyclopentadiene skeleton; epoxy epoxy methyl acrylate copolymer epoxy resin; cyclohexyl maleimide and epoxy epoxy methyl acrylate copolymer epoxy; epoxy Modified polybutadiene rubber derivatives; CTBN modified epoxy resin, etc., but not limited to these. These epoxy resins can be used individually by 1 type or in combination of 2 or more types. Among these, especially phenolic epoxy resin, bisphenol epoxy resin, bisxylenol epoxy resin, bisphenol epoxy resin, bisphenol novolac epoxy resin, naphthalene epoxy resin or These mixtures are preferred.
作為多官能環氧丙烷化合物,有舉例如雙[(3-甲基-3-環氧丙烷甲氧基)甲基]醚、雙[(3-乙基-3-環氧丙烷甲氧基)甲基]醚、1,4-雙[(3-甲基-3-環氧丙烷甲氧基)甲基]苯、1,4-雙[(3-乙基-3-環氧丙烷甲氧基)甲基]苯、(3-甲基-3-環氧丙烷)甲基丙烯酸酯、(3-乙基-3-環氧丙烷)甲基丙烯酸酯、(3-甲基-3-環氧丙烷)甲基丙烯酸甲酯,(3-乙基-3-環氧丙烷)甲基丙烯酸甲酯或此等之寡聚物或共聚合物等之多官能環氧丙烷類之外,亦有舉出環氧丙烷醇與酚醛樹脂、聚(p-羥基苯乙烯)、陽基環型雙酚類、酚醛環狀聚合物類、芳杯類或具有半矽氧烷等之羥基的樹脂之醚化物等。另外,亦舉出具有環氧丙烷環之不飽和單體與烷基(甲基)丙烯酸酯之共聚合物等。 Examples of the polyfunctional propylene oxide compound include bis [(3-methyl-3-glycidyloxy) methyl] ether and bis [(3-ethyl-3-glycidylmethoxy). Methyl] ether, 1,4-bis [(3-methyl-3-glycidyloxy) methyl] benzene, 1,4-bis [(3-ethyl-3-glycidyloxy) (Methyl) methyl] benzene, (3-methyl-3-propylene oxide) methacrylate, (3-ethyl-3-propylene oxide) methacrylate, (3-methyl-3-cyclo Oxypropane) methyl methacrylate, (3-ethyl-3-epoxypropane) methyl methacrylate or polyfunctional propylene oxides such as oligomers or copolymers, etc. Ethers of propylene oxide and phenolic resins, poly (p-hydroxystyrene), cation-based bisphenols, phenolic cyclic polymers, aromatic cups, or resins with hydroxyl groups such as hemisiloxane物 等。 And so on. A copolymer of an unsaturated monomer having a propylene oxide ring and an alkyl (meth) acrylate is also mentioned.
作為在分子中具有複數個環狀乙硫醚基之化合物,有舉出雙酚A型環氧硫化物樹脂等。且,也能夠使用以相同的合成方法來將酚醛型環氧樹脂之環氧基的氧原子取代成硫原子之環氧硫化物樹脂等。如此之分子中具有複數個環狀(硫)***基之熱硬化成分的摻混量,相對於(A)含有羧基之樹脂的羧基1當量為0.6~2.5當量較佳。摻混量為0.6當量以上時,硬化物上難以殘留羧基,且耐熱性、耐鹼性、電氣絕緣性等較良好。另一方面,為2.5當量以下時,低分子量之環狀(硫)***基較難以殘存在乾燥塗膜上,塗膜的強度等較良好。再較佳為0.8~2.0當量。 Examples of the compound having a plurality of cyclic ethyl sulfide groups in the molecule include a bisphenol A type epoxy sulfide resin. In addition, an epoxy sulfide resin or the like in which an oxygen atom of an epoxy group of a phenolic epoxy resin is replaced with a sulfur atom by the same synthetic method can also be used. The blending amount of the thermosetting component having a plurality of cyclic (thio) ether groups in such a molecule is preferably 0.6 to 2.5 equivalents with respect to 1 equivalent of the carboxyl group of the resin containing the carboxyl group (A). When the blending amount is 0.6 equivalent or more, it is difficult for the carboxyl group to remain on the cured product, and heat resistance, alkali resistance, electrical insulation, and the like are good. On the other hand, when it is 2.5 equivalents or less, it is difficult for a low-molecular-weight cyclic (thio) ether group to remain on the dried coating film, and the strength and the like of the coating film are good. It is more preferably 0.8 to 2.0 equivalents.
作為聚氰胺衍生物、苯胍胺衍生物等之胺基樹脂,有舉出羥甲基三聚氰胺化合物、羥甲基苯胍胺化合 物、羥甲基乙快脲化合物以及羥甲基尿素化合物等。 Examples of amine-based resins such as melamine derivatives and benzoguanamine derivatives include methylol melamine compounds and methylol benzoguanamine compounds. Compounds, methylol urea compounds, and methylol urea compounds.
作為異氰酸酯化合物,能夠摻混聚異氰酸酯化合物。作為聚異氰酸酯化合物,有舉出4,4’-二苯基甲烷二異氰酸酯、2,4-二異氰酸甲苯、2,6-二異氰酸甲苯、萘-1,5-二異氰酸酯、o-苯二甲基二異氰酸酯、m-苯二甲基二異氰酸酯以及2,4-甲伸苯基二聚物等之芳香族聚異氰酸酯;四甲烯二異氰酸酯、六亞甲基二異氰酸酯、甲烯二異氰酸酯、三甲基六亞甲基二異氰酸酯、4,4-甲烯雙(環己基異氰酸酯)以及異佛酮二異氰酸酯等之脂肪族聚異氰酸酯;雙環庚烷三異氰酸酯等之脂環式聚異氰酸酯;以及先前舉出的異氰酸酯化合物之加合物、縮二脲體以及異氰脲酸酯體等。 As the isocyanate compound, a polyisocyanate compound can be blended. Examples of the polyisocyanate compound include 4,4'-diphenylmethane diisocyanate, toluene 2,4-diisocyanate, toluene 2,6-diisocyanate, naphthalene-1,5-diisocyanate, o -Aromatic polyisocyanates such as xylylene diisocyanate, m-xylylene diisocyanate, and 2,4-methylenephenyl dimer; tetramethylene diisocyanate, hexamethylene diisocyanate, methylene Aliphatic polyisocyanates such as diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methene bis (cyclohexyl isocyanate), and isophorone diisocyanate; alicyclic polyisocyanates such as dicycloheptane triisocyanate ; And adducts, biuret bodies, and isocyanurate bodies of the isocyanate compounds previously cited.
作為嵌段異氰酸酯化合物,能夠使用異氰酸酯化合物與異氰酸酯嵌段劑之付加反應生成物。作為能夠與異氰酸酯嵌段劑反應之異氰酸酯化合物,有舉例如上述之聚異氰酸酯化合物等。作為異氰酸酯嵌段劑,有舉例如苯酚系嵌段劑;內醯胺系嵌段劑;活性甲烯系嵌段劑;醇系嵌段劑;肟系嵌段劑;硫醇系嵌段劑;醯胺系嵌段劑;亞醯胺系嵌段劑;胺系嵌段劑;咪唑系嵌段劑;亞胺系嵌段劑等。 As the block isocyanate compound, an additive reaction product of an isocyanate compound and an isocyanate blocking agent can be used. Examples of the isocyanate compound capable of reacting with the isocyanate blocking agent include the aforementioned polyisocyanate compounds. Examples of isocyanate blocking agents include phenol-based blocking agents; lactam-based blocking agents; active methylene-based blocking agents; alcohol-based blocking agents; oxime-based blocking agents; thiol-based blocking agents; Imidamine-based block agents; imidamine-based block agents; amine-based block agents; imidazole-based block agents; imine-based block agents and the like.
如此之聚異氰酸酯化合物或嵌段異氰酸酯化合物的摻混量相對於(A)含有羧基之樹脂100質量份為1~100質量份較佳。摻混量為1質量份以上時,能得到充分的塗膜之強韌性。另一方面,為100質量以下時,保存 安定性良好。再較佳為2~70質量份。 The blending amount of such a polyisocyanate compound or a block isocyanate compound is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the resin having a carboxyl group (A). When the blending amount is 1 part by mass or more, sufficient toughness of the coating film can be obtained. On the other hand, when it is 100 mass or less, save Good stability. It is more preferably 2 to 70 parts by mass.
本發明之感光性樹脂組成物中含有(B)氨基甲酸乙酯(甲基)丙烯酸酯以及能夠作為難燃劑使用的含有磷元素之(甲基)丙烯酸酯以外,亦能夠含有其他光聚合性單體。光聚合性單體為分子中具有1個以上乙烯性不飽和基之化合物,並且為藉由活化能射線照射來進行光硬化後,將前述(A)含有羧基之樹脂不溶化或者幫助不溶化於鹼水溶液者。 The photosensitive resin composition of the present invention contains (B) urethane (meth) acrylate and phosphorus element-containing (meth) acrylate which can be used as a flame retardant, and can also contain other photopolymerizable properties. monomer. The photopolymerizable monomer is a compound having one or more ethylenically unsaturated groups in the molecule, and is used to inactivate the resin containing the carboxyl group (A) or to assist insolubilization in an alkaline aqueous solution after photocuring by activation energy ray irradiation. By.
作為用來作為其他光聚合性單體之化合物,能夠使用習知者之任一。例如能夠使用慣用習知之聚酯(甲基)丙烯酸酯、聚醚(甲基)丙烯酸酯、碳酸鹽(甲基)丙烯酸酯、環氧(甲基)丙烯酸酯,具體來說,有舉出2-羥乙基丙烯酸酯、2-羥丙基丙烯酸酯等之羥烷基丙烯酸酯類;乙烯二醇、甲氧基四乙烯二醇、聚乙烯二醇、丙二醇等之乙二醇的二丙烯酸酯類;N,N-二甲基丙烯醯胺、N-羥甲基丙烯醯胺、N,N-二甲胺基丙基丙烯醯胺等之丙烯醯胺類;N,N-二甲胺基乙基丙烯酸酯、N,N-二甲胺基丙基丙烯酸酯等之胺基烷基丙烯酸酯類;己二醇、三羥甲丙烷、季戊四醇、二季戊四醇、參-羥乙基異氰酯等之多價醇或此等之氧乙烷加成物、氧化丙烯加成物或ε-己內酯加成物等之多價丙烯酸酯類;苯氧基丙烯酸酯、雙酚A二丙烯酸酯以及此等之苯酚類的氧乙烷加成物或氧化丙烯加成物等之多價 丙烯酸酯類;丙三醇二氧化丙烯醚、丙三醇三環氧丙基醚、三羥甲丙烷三環氧丙基醚、三縮水甘油基異三聚氰酸酯等之環氧丙基醚之多價丙烯酸酯類;不限於上述,也有舉出將聚醚多元醇、聚碳酸酯二醇、羥基末端聚丁二烯、聚酯多元醇等之多元醇直接進行丙烯酸酯化之丙烯酸酯類以及對應於三聚氰胺丙烯酸酯以及/或上述丙烯酸酯之各丙烯酸甲酯類等。其他光聚合性單體能夠單獨使用1種或組合2種以上來使用。 As the compound used as the other photopolymerizable monomer, any one of known ones can be used. For example, conventionally known polyester (meth) acrylates, polyether (meth) acrylates, carbonate (meth) acrylates, and epoxy (meth) acrylates can be used. Specific examples include 2 -Hydroxyalkyl acrylates such as hydroxyethyl acrylate and 2-hydroxypropyl acrylate; ethylene glycol diacrylates of ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, propylene glycol, etc. Class; N, N-dimethylacrylamide, N-methylmethacrylamide, N, N-dimethylaminopropylacrylamide, etc .; N, N-dimethylamine Amino alkyl acrylates such as ethyl acrylate, N, N-dimethylaminopropyl acrylate, etc .; hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, p-hydroxyethyl isocyanate, etc. Polyvalent alcohols or polyvalent acrylates such as oxyethane adducts, propylene oxide adducts or ε-caprolactone adducts; phenoxy acrylates, bisphenol A diacrylates, and The valence of these phenolic oxyethane adducts or propylene oxide adducts Acrylates; glycerol dipropylene oxide, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl isotricyanate, etc. Polyvalent acrylates; not limited to the above, there are also acrylates in which polyhydric alcohols such as polyether polyols, polycarbonate diols, hydroxyl-terminated polybutadiene, and polyester polyols are directly acrylated And methyl acrylates and the like corresponding to melamine acrylate and / or the above acrylate. Other photopolymerizable monomers can be used individually by 1 type or in combination of 2 or more types.
包含前述(B)氨基甲酸乙酯(甲基)丙烯酸酯以及能夠作為難燃劑使用之含有磷元素之(甲基)丙烯酸酯的光聚合性單體之總量相對於前述(A)含有羧基之樹脂100質量份,較佳為10~250質量份,再較佳為10~200質量份。為10質量份以上時,光硬化性較良好,且容易藉由活化能射線照射後之鹼顯像來形成圖型。另一方面,為250質量份以下時,對於鹼水溶液的溶解性較良好,能夠抑制解像性的降低。 The total amount of the photopolymerizable monomer containing the (B) urethane (meth) acrylate and the phosphorus-containing (meth) acrylate which can be used as a flame retardant is contained in the (A) containing a carboxyl group The resin is 100 parts by mass, preferably 10 to 250 parts by mass, and still more preferably 10 to 200 parts by mass. When it is 10 parts by mass or more, the photocurability is good, and the pattern is easily formed by alkali development after irradiation with active energy rays. On the other hand, when it is 250 parts by mass or less, the solubility in an alkaline aqueous solution is good, and a decrease in resolution can be suppressed.
較多的高分子材料開始有一次的氧化之後,會接著發生連續的氧化惡化,並造成高分子素材的機能降低,因此為了要防止本發明之感光性樹脂組成物的氧化,能夠添加(1)會使所產生的自由基無效化之自由基補充劑以及/或(2)將產生的過氧化物分解成為無害物質,並且不會產生新的自由基之過氧化物分解劑等之抗氧化劑。 After a large number of polymer materials begin to be oxidized once, continuous oxidative deterioration will continue to occur, and the function of the polymer material will be reduced. Therefore, in order to prevent oxidation of the photosensitive resin composition of the present invention, it is possible to add (1) Antioxidants such as radical supplements that invalidate the generated radicals and / or (2) decomposition of the generated peroxides into harmless substances, and do not generate new radicals such as peroxide decomposition agents.
作為具有自由基補充劑功能的抗氧化劑,作為具體的化合物,有舉出氫醌、4-tert-丁基兒茶酚、2-t-丁基氫醌、氫醌單甲基醚、2,6-二-t-丁基-p-甲酚、2,2-甲烯雙-(4-甲基-6-t-丁基苯酚)、1,1,3-參(2-甲基-4-羥基-5-t-丁基苯基)丁烷、1,3,5-三甲基-2,4,6-參(3,5-二-t-丁基-4-羥基苄基)苯、1,3,5-參(3’,5’二-t-丁基-4-羥基苄基)-S-三氮雜苯-2,4,6-(1H,3H,5H)三酮等之苯酚系、甲基醌、苯醌等之醌系化合物、雙(2,2,6,6-四甲基-4-哌啶基)-癸二酸酯、硫二苯胺等之胺系化合物等。 Specific examples of the antioxidant having a function of a free radical supplement include hydroquinone, 4-tert-butylcatechol, 2-t-butylhydroquinone, hydroquinone monomethyl ether, 2, 6-di-t-butyl-p-cresol, 2,2-methenebis- (4-methyl-6-t-butylphenol), 1,1,3-ginseng (2-methyl- 4-hydroxy-5-t-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-para (3,5-di-t-butyl-4-hydroxybenzyl) ) Benzene, 1,3,5-ginseng (3 ', 5'di-t-butyl-4-hydroxybenzyl) -S-triazabenzene-2,4,6- (1H, 3H, 5H) Phenols such as triones, quinones such as methylquinone, benzoquinone, bis (2,2,6,6-tetramethyl-4-piperidinyl) -sebacate, thiodiphenylamine, etc. Amine compounds and the like.
自由基補充劑亦可為市售者,有舉例如ADKSTAB AO-30、ADKSTAB AO-330、ADKSTAB AO-20、ADKSTAB LA-77、ADKSTAB LA-57、ADKSTAB LA-67、ADKSTAB LA-68、ADKSTAB LA-87(以上,ADEKA公司製,商品名)、IRGANOX1010、IRGANOX1035、IRGANOX1076、IRGANOX1135、TINUVIN 111FDL、TINUVIN 123、TINUVIN 144、TINUVIN 152、TINUVIN 292、TINUVIN 5100(以上,BASF Japan公司製,商品名)等。作為具有過氧化物分解劑功能的抗氧化劑,作為具體的化合物,有舉出三苯基亞磷酸酯等之磷系化合物、季戊四醇四月桂基硫基丙酸酯、二月桂基硫基二丙酸酯、二硬脂醯3,3’-硫基二丙酸酯等之硫系化合物等。 Free radical supplements can also be commercially available, such as ADKSTAB AO-30, ADKSTAB AO-330, ADKSTAB AO-20, ADKSTAB LA-77, ADKSTAB LA-57, ADKSTAB LA-67, ADKSTAB LA-68, ADKSTAB LA-87 (above, manufactured by ADEKA Corporation, trade name), IRGANOX1010, IRGANOX1035, IRGANOX1076, IRGANOX1135, TINUVIN 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, TINUVIN 5100 (above, manufactured by BASF Japan, trade name) Wait. Specific examples of the antioxidant having a function of a peroxide decomposer include phosphorus-based compounds such as triphenylphosphite, pentaerythritol tetralaurylthiopropionate, and dilaurylthiodipropionic acid. Sulfur compounds such as esters, distearyl 3,3'-thiodipropionate and the like.
過氧化物分解劑亦可為市售者,有舉例如,ADKSTAB TPP(ADEKA公司製,商品名),Mark AO-412S(ADEKA公司製,商品名),SUMILIZER TPS(住友化 學公司製,商品名)等。 The peroxide decomposer may also be commercially available. For example, ADKSTAB TPP (made by ADEKA Corporation, trade name), Mark AO-412S (made by ADEKA Corporation, trade name), SUMILIZER TPS (Sumitomo Chemical) Company system, trade name).
上述之抗氧化劑能夠單獨使用1種或組合2種以上來使用。 These antioxidants can be used alone or in combination of two or more.
本發明之感光性樹脂組成物能夠使用用於(A)含有羧基之樹脂的合成或組成物的調製,或者用於基板或用來塗布於載體膜的黏度調整之有機溶劑。作為如此之有機溶劑,能夠舉出酮類、芳香族烴類、乙二醇醚類、乙二醇醚乙酸酯類、酯類、醇類、脂肪族烴、石油系溶劑等。更具體來說,有甲乙酮、環己酮等之酮類;甲苯、二甲苯、四甲苯等之芳香族烴類;賽珞蘇、甲基賽珞蘇、丁基賽珞蘇、卡必醇、甲基卡必醇、丁基卡必醇、丙二醇單甲基醚、二丙二醇單甲基醚、二丙二醇二乙基醚、三乙烯二醇單乙基醚等之乙二醇醚類;乙酸乙酯、乙酸丁酯、二丙二醇甲基醚乙酸酯、丙二醇甲基醚乙酸酯、丙二醇乙基醚乙酸酯、丙二醇丁基醚乙酸酯等之酯類;乙醇、丙醇、乙烯二醇、丙二醇等之醇類;辛烷、癸烷等之脂肪族烴;石油醚、石油腦、氫化石油腦、溶劑石油腦等之石油系溶劑等。如此之有機溶劑能夠單獨使用1種或組合2種以上來使用。 The photosensitive resin composition of the present invention can be used for (A) the synthesis of a carboxyl group-containing resin or the preparation of a composition, or an organic solvent for adjusting the viscosity of a substrate or a carrier film. Examples of such organic solvents include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, and petroleum solvents. More specifically, there are ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetra toluene; cyperidine, methyl cyperidine, butyl cyperidine, carbitol, Glycol ethers such as methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, and triethylene glycol monoethyl ether; ethyl acetate Ester, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol butyl ether acetate and the like; ethanol, propanol, ethylene diacetate Alcohols such as alcohols and propylene glycol; aliphatic hydrocarbons such as octane and decane; petroleum-based solvents such as petroleum ether, petroleum brain, hydrogenated petroleum brain, and solvent petroleum brain. Such an organic solvent can be used individually by 1 type or in combination of 2 or more types.
本發明之感光性樹脂組成物中亦可含有藉由加熱使組 成物之硬化物的L*a*b*表色系統中的b*值減少的增白用添加劑。於此,增白用添加劑意指能夠增加組成物的硬化物白色度,使其看起來不會變色者。 The photosensitive resin composition of the present invention may further contain a whitening additive that reduces the b * value in the L * a * b * color system of the composition by heating. Here, the whitening additive means a substance capable of increasing the whiteness of the hardened material of the composition so that it does not appear discolored.
於此,本案說明書中,藉由加熱使組成物之硬化物的b*值減少意指最初加熱組成物之硬化物時,b*值會減少,且不包含第2次以後的加熱。且,此時的加熱溫度意指實質上將組成物以焊料實裝時的溫度,具體來說為200℃以上,例如220~370℃。一般的焊料回融步驟是在約260℃下僅進行1次。為增白用添加劑時,在組成物的硬化溫度之約150℃左右的溫度下加熱,不會產生b*值的減少。 Here, in the specification of the present case, the decrease in the b * value of the hardened material of the composition by heating means that when the hardened material of the composition is first heated, the b * value decreases, and the second and subsequent heatings are not included. In addition, the heating temperature at this time means the temperature when the composition is substantially mounted with solder, and is specifically 200 ° C or higher, for example, 220 to 370 ° C. The general solder remelting step is performed only once at about 260 ° C. In the case of an additive for whitening, heating at a temperature of about 150 ° C of the composition's curing temperature does not cause a decrease in b * value.
作為增白用添加劑,能夠適當地使用具有苯并噁唑系骨格者,其中,包含1種以上具有下述式(I) As the whitening additive, those having a benzoxazole-based skeleton can be suitably used. Among them, one or more of them have the following formula (I).
所表示之化合物中的任1種,或2種以上,尤其是3種之混合物。且,作為增白用添加劑,分解溫度為400℃以上者較適當。於此,作為將增白用添加劑的分解溫度設在400℃以上的理由,是為了要防止在回融步驟中,有在350℃前後處理的規定,其熱負荷所帶來的添加劑自體之分解。針對分解溫度的上限值並無特別限制,但有例如400℃~600℃。 Any one of the compounds shown, or two or more, especially a mixture of three. In addition, as a whitening additive, a decomposition temperature of 400 ° C. or higher is suitable. Here, the reason for setting the decomposition temperature of the whitening additive at 400 ° C or higher is to prevent the temperature of the additive from being caused by heat load during the remelting step. break down. The upper limit of the decomposition temperature is not particularly limited, but there are, for example, 400 ° C to 600 ° C.
作為上述增白用添加劑之摻混量,以相對於(A)含有羧基之樹脂100質量份為0.01~60質量份較佳,再較佳為0.1~40質量份。 The blending amount of the whitening additive is preferably 0.01 to 60 parts by mass with respect to 100 parts by mass of the resin containing a carboxyl group (A), and more preferably 0.1 to 40 parts by mass.
且,本發明之感光性樹脂組成物亦可包含施予表面處理的光激發性無機充填劑。施予表面處理的光激發性無機充填劑意指對光激發性無機充填劑施予無機成分 或酸性液體的表面處理。藉由使用施予表面處理的光激發性無機充填劑,再進一步滿足後述pH值之相關條件,能夠在其硬化塗膜中實現高反射率。使用施予表面處理者作為光激發性無機充填劑是因為藉由施予表面處理,光激發性無機充填劑之表面會形成不溶性或難溶性的反應生成物,且其表面的耐水性會猛躍地提升,在水存在之條件下,也能夠得到在長期間維持高反射率的效果。 In addition, the photosensitive resin composition of the present invention may include a photo-excitable inorganic filler that has been subjected to a surface treatment. Applying a photo-excitation inorganic filler to a surface treatment means applying an inorganic component to the photo-excitation inorganic filler Or surface treatment of acidic liquids. By using a photo-excitable inorganic filler that has been subjected to a surface treatment, and further satisfying conditions related to the pH value described later, a high reflectance can be achieved in the cured coating film. The reason why the surface-treated inorganic filler is used as the photo-excitation inorganic filler is that by applying the surface treatment, the surface of the photo-excitation inorganic filler will form an insoluble or hardly soluble reaction product, and the water resistance of the surface will be greatly improved. The effect of ground lifting is to maintain high reflectance for a long period of time even in the presence of water.
作為光激發性無機充填劑,有舉出鋁酸鹽鍶、硫化鋅等,尤其是能夠適當地使用鋁酸鹽鍶。此等光激發性無機充填劑亦可僅使用1種,或者混合2種以上來使用。且,作為表面處理所使用的無機成分,有舉出二氧化矽(玻璃)、氧化鋁、氧化鋯等。作為使用無機成分之表面處理的方法,能夠使用周知的方法,並無特別限定。 Examples of the photo-excitable inorganic filler include strontium aluminate, zinc sulfide, and the like. In particular, strontium aluminate can be suitably used. These photo-excitable inorganic fillers may be used alone or in combination of two or more. In addition, examples of the inorganic component used in the surface treatment include silicon dioxide (glass), alumina, and zirconia. As a method of surface treatment using an inorganic component, a well-known method can be used, and it does not specifically limit.
另外,作為酸性液體,能夠使用選自硝酸、鹽酸、碳酸、硫酸、亞硫酸、矽酸、硼酸、磷酸、亞磷酸、聚磷酸、第1磷酸鈉、六偏磷酸鈉、乙酸、酪酸、丙酸、辛酸、月桂酸、十八烷酸、丙烯酸、甲基丙烯酸、草酸、丁二酸、檸檬酸、蘋果酸、酒石酸、己二酸、壬二酸、癸二酸、苯二甲酸、水楊酸、安息香酸、没食子酸、苯酚、萘甲酸、甲苯磺酸、苯磺酸、偏磷酸、牛磺酸、抗壞血酸、矽烷醇酸、膦酸、巴豆酸、馬來酸、乳酸等之酸或此等酸之鹽類,例如鉀鹽、鈉鹽、銨鹽、以及酸酐等之酸產生化合物中之酸性化合物,其中,使用磷酸、亞磷酸、聚磷酸、第1磷酸鈉等之磷酸類以及此等之鹽類所構 成之磷酸系化合物、以及硫酸較佳,磷酸系化合物特別佳。無機成分以及酸性液體能夠單獨使用任1種,或使用組合2種以上者。 As the acidic liquid, a member selected from the group consisting of nitric acid, hydrochloric acid, carbonic acid, sulfuric acid, sulfurous acid, silicic acid, boric acid, phosphoric acid, phosphorous acid, polyphosphoric acid, first sodium phosphate, sodium hexametaphosphate, acetic acid, butyric acid, and propionic acid can be used. , Caprylic acid, lauric acid, octadecanoic acid, acrylic acid, methacrylic acid, oxalic acid, succinic acid, citric acid, malic acid, tartaric acid, adipic acid, azelaic acid, sebacic acid, phthalic acid, salicylic acid , Benzoic acid, gallic acid, phenol, naphthoic acid, toluenesulfonic acid, benzenesulfonic acid, metaphosphoric acid, taurine, ascorbic acid, silanolic acid, phosphonic acid, crotonic acid, maleic acid, lactic acid, or the like Acid salts such as potassium salts, sodium salts, ammonium salts, and acid anhydride compounds among acid-generating compounds, among which phosphoric acids such as phosphoric acid, phosphorous acid, polyphosphoric acid, and first sodium phosphate and the like are used. Salt structure The resulting phosphoric acid-based compound and sulfuric acid are preferred, and the phosphoric acid-based compound is particularly preferred. The inorganic component and the acidic liquid can be used either alone or in combination of two or more.
於此,酸性液體的表面處理能夠使用上述酸性液體,並於pH值為3以下之條件下來行,有舉例如於含有酸性液體之水溶液中浸漬光激發性無機充填劑之方法,對光激發性無機充填劑噴霧含有酸性液體之水溶液之方法,在高濕度的環境中使光激發性無機充填劑的表面與酸性液體接觸之方法。此等之方法中,於含有酸性液體之水溶液中浸漬光激發性無機充填劑之方法,以操作簡單並能夠有效率地反應之觀點來看,較適當。 Here, the surface treatment of the acidic liquid can use the above-mentioned acidic liquid, and can be performed under the condition of a pH value of 3 or less. For example, a method of immersing a photo-excitable inorganic filler in an aqueous solution containing an acidic liquid can be used. A method of spraying an inorganic filler with an aqueous solution containing an acidic liquid, and a method of contacting the surface of the photo-excitable inorganic filler with the acidic liquid in a high-humidity environment. Among these methods, a method of immersing a photo-excitable inorganic filler in an aqueous solution containing an acidic liquid is suitable from the viewpoint of simple operation and efficient reaction.
具體來說,首先,準備相對於光激發性無機充填劑為1~1000質量倍左右,較佳為2~100質量倍左右,再較佳為3~10質量倍左右的水,將上述酸性液體溶解使其成為0.01~30質量%左右,較佳為0.5~10質量%左右之濃度。此時,以調整酸性液體之溶解能為目的,能夠將上述水的一部分替換成甲醇、乙醇、丙酮、二氧雜環、二甲基甲醯胺(DMF)、二甲亞碸(DMSO)等之水溶性有機溶劑。此時有機溶劑的使用量並無特別限定,只要在不阻礙光激發性無機充填劑之金屬氧化物與酸性液體之反應的範圍下即可,但通常是設在較使用之水的容量少的量。且,此水溶液中,為了提升光激發性無機充填劑的分散性,亦可添加界面活性劑。界面活性劑的種類或使用量等能夠因應所使用的光激發性無機充填劑之種類以及量來作適當地 調整。 Specifically, first, water of about 1 to 1000 mass times, preferably about 2 to 100 mass times, and still more preferably about 3 to 10 mass times of the photoactive inorganic filler is prepared, and the above-mentioned acidic liquid is prepared. It is dissolved so as to have a concentration of about 0.01 to 30% by mass, preferably about 0.5 to 10% by mass. At this time, for the purpose of adjusting the dissolving energy of the acidic liquid, a part of the above water can be replaced with methanol, ethanol, acetone, dioxane, dimethylformamide (DMF), dimethylformamide (DMSO), etc. A water-soluble organic solvent. In this case, the amount of the organic solvent used is not particularly limited, as long as it does not hinder the reaction between the metal oxide of the photo-excitable inorganic filler and the acidic liquid, but it is usually set at a lower capacity than the water used. the amount. In addition, a surfactant may be added to this aqueous solution in order to improve the dispersibility of the photo-excitable inorganic filler. The type and amount of the surfactant can be appropriately determined according to the type and amount of the photo-excitable inorganic filler used. Adjustment.
接著,在包含酸性液體的水溶液中添加光激發性無機充填劑,藉由攪拌使其均勻地分散,使酸性液體與光激發性無機充填劑的金屬氧化物進行反應。針對此時的處理溫度並無特別限定,但通常能夠將液體溫度設在20℃左右以上,較佳為50℃~未滿沸點之溫度範圍,處理時間能夠設在0.5~120分鐘,較佳為10~60分鐘。 Next, a photo-excitable inorganic filler is added to an aqueous solution containing an acidic liquid, and uniformly dispersed by stirring, so that the acidic liquid and the metal oxide of the photo-excitable inorganic filler react. The processing temperature at this time is not particularly limited, but usually the liquid temperature can be set to about 20 ° C or higher, preferably 50 ° C to a boiling point temperature range, and the processing time can be set to 0.5 to 120 minutes, preferably 10 ~ 60 minutes.
上述酸性液體的表面處理後,能夠使用選自鹼或鹼產生化合物中至少一種鹼性化合物,來施予鹼處理。鹼處理是在pH值4~9,較適當是在pH值4~7之條件下來進行。藉由施予鹼處理,使用上述酸性液體的表面處理所得之光激發性無機充填劑的耐水性之耐久性會提升,即使在高溫下長期間使用,也能夠保持其耐水性。這是認為光激發性無機充填劑表面上所形成的反應生成物會因為鹼處理而被變性得更加強固。作為鹼處理所使用的鹼,有使用氫氧化鈉、氫氧化鋰、氫氧化鈣、氫氧化鉀、氫氧化鍶、氨等,但較適當為使用氫氧化鈉。且,作為鹼產生化合物,有使用第二磷酸鈉、第三磷酸鈉、六偏磷酸鈉、乙酸鈉、酸化鍶等,但較適當為使用第三磷酸鈉。進一步能夠使用單乙醇胺、三乙醇胺、胍、硬脂醯胺、砒啶等之有機鹼性化合物。 After the surface treatment of the acidic liquid, at least one basic compound selected from the group consisting of an alkali or a base-generating compound can be used for the alkali treatment. Alkali treatment is carried out at a pH of 4-9, and more suitably at a pH of 4-7. By applying an alkali treatment, the water-resistant inorganic filler obtained by the surface treatment of the above-mentioned acidic liquid has improved water resistance and durability, and can maintain its water resistance even when used at a high temperature for a long period of time. This is considered to be because the reaction product formed on the surface of the photo-excitable inorganic filler is denatured and strengthened more by alkali treatment. Examples of the alkali used in the alkali treatment include sodium hydroxide, lithium hydroxide, calcium hydroxide, potassium hydroxide, strontium hydroxide, and ammonia. However, sodium hydroxide is more suitably used. In addition, as the base-generating compound, a second sodium phosphate, a third sodium phosphate, sodium hexametaphosphate, sodium acetate, strontium acid, and the like are used, but a third sodium phosphate is more suitably used. Further, organic basic compounds such as monoethanolamine, triethanolamine, guanidine, stearylamine, and pyridine can be used.
針對鹼處理之手段並無特別限制,能夠例如由以下來進行。亦即,能夠在上述酸性液體的處理後,去除上清液,再新添加適量的水。接著,以攪拌機等一邊攪 拌一邊慢慢地添加上述鹼性化合物,將pH值調整至4~9來進行。針對此時的處理溫度並無特別限制,但通常將液體溫度設在20℃左右以上,較適當為50℃~未滿沸點之溫度範圍。處理時間通常設在0.5~120分鐘,較適當為10~60分鐘。 The means for alkali treatment is not particularly limited, and can be performed, for example, as follows. That is, after the treatment of the acidic liquid, the supernatant can be removed, and an appropriate amount of water can be newly added. Next, stir with a blender, etc. Slowly add the above-mentioned basic compound while stirring, and adjust the pH to 4-9. The processing temperature at this time is not particularly limited, but the liquid temperature is usually set to about 20 ° C or higher, and a temperature range of 50 ° C to a full boiling point is more suitable. The processing time is usually set at 0.5 to 120 minutes, and more suitably 10 to 60 minutes.
上述鹼處理後,藉由去除上清液,並過濾水洗之後,使其充分乾燥,能夠得到目的之施予表面處理的光激發性無機充填劑。此時之乾燥條件並無特別限定,但通常在20℃以上的溫度下乾燥2小時以上即可。經表面處理的光激發性無機充填劑,能夠因應必要,藉由過篩而得到粉末狀之狀態。如此所得之施予表面處理的光激發性無機充填劑,相對於40℃之水100g的溶解度為未滿1g,且由於具有耐熱性,故能夠長時間地維持非常良好的耐水性。 After the alkali treatment, the supernatant liquid is removed, and after filtering and washing with water, it is sufficiently dried to obtain the intended photo-excitable inorganic filler for surface treatment. The drying conditions at this time are not particularly limited, but it is usually sufficient to dry at a temperature of 20 ° C or higher for 2 hours or more. The surface-treated photoexcitation inorganic filler can be sieved to obtain a powdery state as necessary. The surface-excited photo-excited inorganic filler thus obtained has a solubility of less than 1 g with respect to 100 g of water at 40 ° C. and has heat resistance, so it can maintain very good water resistance for a long time.
且,作為施予表面處理的光激發性無機充填劑,將光激發性無機充填劑10g加入丙酮50g中,取出一次不溶成分,之後,將取出的一次不溶成分加入氯仿50g中,取出二次不溶成分,之後,進一步將取出的二次不溶成分加入純水10g中,在30℃下攪拌1週後所得之液體的pH值為6~12,以得到高反射率之點來說較佳。 In addition, as a photo-excitation inorganic filler to be subjected to a surface treatment, 10 g of the photo-excitation inorganic filler was added to 50 g of acetone, and once the insoluble component was taken out, after that, the taken-out primary insoluble component was added to 50 g of chloroform, and the secondary insoluble was taken out. Then, the extracted secondary insoluble component is further added to 10 g of pure water, and the pH value of the liquid obtained after stirring at 30 ° C for 1 week is 6-12, which is preferable in terms of obtaining high reflectance.
作為光激發性無機充填劑的摻混量,相對於(A)羧基樹脂100質量份為例如0.1~500質量份。 The compounding quantity of a photoexcitation inorganic filler is 0.1-500 mass parts with respect to 100 mass parts of (A) carboxy resins, for example.
本發明之感光性樹脂組成物中,能夠因應必要,進一步摻混熱硬化觸媒、氨基甲酸乙酯化觸媒、環氧 硬化劑熱可塑性樹脂、嵌段共聚合物、填料、黏結劑聚合物、合成橡膠、密著促進劑、抗氧化劑、紫外線吸收劑、熱聚合禁止劑等成分。此等,能夠使用在電子材料的領域中所習知之物。且,本發明之感光性樹脂組成物中,能夠摻混微粉二氧化矽、水滑石、有機皂土、高嶺石等之公知慣用的增黏劑、矽氧系、氟系、高分子系等之消泡劑以及/或均染劑、咪唑系、噻唑系、***系等之矽烷偶合劑、除鏽劑等之習知慣用的添加劑類。 In the photosensitive resin composition of the present invention, a thermal curing catalyst, a urethane-based catalyst, and an epoxy resin can be further blended as necessary. Hardener thermoplastic resin, block copolymer, filler, adhesive polymer, synthetic rubber, adhesion promoter, antioxidant, ultraviolet absorber, thermal polymerization inhibitor and other components. These can be used in the field of electronic materials. In addition, the photosensitive resin composition of the present invention can be blended with well-known and commonly used thickeners such as silica, hydrotalcite, organic bentonite, kaolinite, etc., silica-based, fluorine-based, and polymer-based. Defoaming agents and / or leveling agents, silane coupling agents such as imidazole-based, thiazole-based, triazole-based, and rust-removing agents are conventional and commonly used additives.
本發明之感光性樹脂組成物有用在印刷配線板的迴路圖型之保護層形成,尤其是有用在永久絕緣被膜的形成。其中,有用在作為以阻焊或背膠膜為首之形成最外層部所需之材料。尤其是,有用來作為有實裝LED等之發光元件之可撓式印刷配線板用之阻焊或背膠膜的材料。具備本發明之感光性樹脂組成物所形成之阻焊的可撓式印刷配線板能夠適當地使用在LED照明等之背板。且,本發明之感光性樹脂組成物不僅使用在可撓式印刷配線板,亦可使用在剛性印刷配線板。且,本發明之感光性樹脂組成物亦可使用在焊料壩之形成。 The photosensitive resin composition of the present invention is useful for forming a protective layer of a circuit pattern of a printed wiring board, and is particularly useful for forming a permanent insulating film. Among them, it is useful as a material required for forming an outermost portion including a solder resist or a self-adhesive film. In particular, there are materials for solder masks or adhesive films for flexible printed wiring boards having light emitting elements such as LEDs mounted thereon. The flexible printed wiring board provided with the solder resist formed by the photosensitive resin composition of this invention can be used suitably for a backboard of LED lighting etc. In addition, the photosensitive resin composition of the present invention can be used not only for flexible printed wiring boards, but also for rigid printed wiring boards. The photosensitive resin composition of the present invention can also be used for forming a solder dam.
本發明之感光性樹脂組成物能夠為具備載體膜(支持體)、與形成在該載體膜上的上述感光性樹脂組成物所構成之層的乾膜形態。在乾膜化時,能夠將本發明之感光性樹脂組成物以上述有機溶劑稀釋,並調整成適當的黏度,並以點塗布機、片狀塗布機、刀刃塗布機、桿狀塗布機、擠壓塗布機、反轉塗布機、轉印滾筒塗布機、凹版 塗布機、噴霧塗布機等以均勻地厚度塗布在載體膜上,且通常在50~130℃之溫度下乾燥1~30分鐘後而得到膜。針對塗布膜厚並無特別限制,一般來說,在乾燥後之膜厚以1~150μm,較佳以10~60μm之範圍中進行適當地選擇。 The photosensitive resin composition of the present invention can be in the form of a dry film including a carrier film (support) and a layer composed of the photosensitive resin composition formed on the carrier film. When the film is dried, the photosensitive resin composition of the present invention can be diluted with the above-mentioned organic solvent, adjusted to an appropriate viscosity, and applied by a spot coater, a sheet coater, a blade coater, a rod coater, or an extruder. Pressure coater, reverse coater, transfer roll coater, gravure A coater, spray coater, etc. are coated on the carrier film with a uniform thickness, and usually dried at a temperature of 50 to 130 ° C for 1 to 30 minutes to obtain a film. There is no particular limitation on the coating film thickness. Generally, the film thickness after drying is appropriately selected from the range of 1 to 150 μm, preferably 10 to 60 μm.
作為載體膜,有使用塑膠薄膜,且使用聚乙二醇對苯二甲酸酯等之聚酯薄膜、聚亞醯胺薄膜、聚醯胺醯亞胺薄膜、聚丙烯薄膜、聚苯乙烯薄膜等之塑膠薄膜較佳。針對載體膜的厚度並無特別限制,但一般來說,以10~150μm之範圍中進行適當地選擇。 As the carrier film, there are polyester films using polyethylene film, polyethylene glycol terephthalate, etc., polyimide film, polyimide film, polypropylene film, polystyrene film, etc. Plastic film is preferred. There is no particular limitation on the thickness of the carrier film, but in general, it is appropriately selected in the range of 10 to 150 μm.
在載體膜上將本發明之感光性樹脂組成物成膜後,進一步以防止灰塵附著在膜的表面上等之目的來說,在膜的表面層合能夠剝離的覆蓋薄膜較佳。作為能夠剝離的覆蓋薄膜,能夠使用例如聚乙烯薄膜、聚四氟乙烯薄膜、聚丙烯薄膜、經表面處理的紙等,且剝離覆蓋薄膜時,膜與覆蓋薄膜之接著力比膜與載體膜之接著力小者即可。 After forming the photosensitive resin composition of the present invention on a carrier film, it is preferable to laminate a peelable cover film on the surface of the film for the purpose of preventing dust from adhering to the surface of the film. As the peelable cover film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, or the like can be used. When peeling the cover film, the adhesion force between the film and the cover film is greater than that of the film and the carrier film Then the person with the smaller force can do it.
本發明之感光性樹脂組成物,例如以上述有機溶劑調整成塗布方法所適合的黏度,並在基材上以浸漬塗布法、流型塗布法、滾軸塗布法、桿塗布法、網印法、簾狀塗布法等之方法來塗布,並在約60~100℃之溫度下使組成物中所包含的有機溶劑揮發乾燥(暫時乾燥),藉此能夠形成不剝落之塗膜。且,為將上述組成物塗布於載體膜上,使其乾燥並作為薄膜而回捲之乾膜時,以貼合機等在基材上貼合使感光性樹脂組成物層與基材接觸之後,藉 由剝落載體膜,能夠形成樹脂絕緣層。 The photosensitive resin composition of the present invention is adjusted, for example, with the above-mentioned organic solvent to a viscosity suitable for the coating method, and the substrate is subjected to a dip coating method, a flow coating method, a roll coating method, a rod coating method, or a screen printing method. And a curtain coating method, and the organic solvent contained in the composition is evaporated to dryness (temporary drying) at a temperature of about 60 to 100 ° C., thereby forming a coating film that does not peel off. In addition, in order to apply the above composition to a carrier film, dry it, and roll it back as a thin film, the substrate is pasted with a laminator or the like and the photosensitive resin composition layer is brought into contact with the substrate. ,borrow By peeling the carrier film, a resin insulating layer can be formed.
作為上述基材,能夠舉出預先形成迴路之印刷配線板或可撓式印刷配線板之外,亦能夠舉出用使用酚醛紙、環氧紙、玻璃布環氧、玻璃聚亞醯胺、玻璃布/不織布環氧、玻璃布/紙環氧、合成纖維環氧、使用氟.聚乙烯.聚苯醚、聚氧化二甲苯.氰酸酯等之高周波迴路用覆銅層合板等之材質者中所有等級(FR-4等)的覆銅層合板、其他聚亞醯胺薄膜、PET薄膜、玻璃基板、陶瓷基板、晶元板等。 Examples of the substrate include a printed wiring board or a flexible printed wiring board in which a circuit is formed in advance, and examples thereof include the use of phenolic paper, epoxy paper, glass cloth epoxy, glass polyurethane, and glass. Cloth / non-woven epoxy, glass cloth / paper epoxy, synthetic fiber epoxy, using fluorine. Polyethylene. Polyphenylene oxide, polyoxyxylene. All grades (FR-4, etc.) of copper-clad laminates such as cyanate ester copper-clad laminates for high-frequency circuit circuits, other polyurethane films, PET films, glass substrates, ceramic substrates, wafers Wait.
在塗布本發明之感光性樹脂組成物後所進行的揮發乾燥能夠使用熱風循環式乾燥爐、IR爐、加熱板、對流烘箱等(使用具備蒸氣之空氣加熱方式的熱源,使乾燥機內的熱風向流接觸之方法以及以噴嘴朝向支持體吹出的方式)來進行。 Volatile drying after coating the photosensitive resin composition of the present invention can be performed using a hot-air circulation type drying oven, IR furnace, heating plate, convection oven, etc. (using a heat source with air heating method including steam to make hot air in the dryer The method of direct flow contact and the method in which the nozzle is blown toward the support) are performed.
本發明之感光性樹脂組成物含有熱硬化成分時,能夠藉由加熱至例如約140~180℃之溫度後使其熱硬化,使含有上述(A)之羧基的樹脂中之羧基與熱硬化成分反應,形成耐熱性、耐藥品性、耐吸濕性、密著性、電氣特性等之各種特性優異的硬化塗膜。 When the photosensitive resin composition of the present invention contains a thermosetting component, the carboxyl group and the thermosetting component in the resin containing the carboxyl group (A) can be thermally cured by heating to a temperature of, for example, about 140 to 180 ° C. The reaction forms a cured coating film excellent in various properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical characteristics.
藉由對塗布本發明之感光性樹脂組成物並揮發乾燥溶劑之後所得的塗膜進行曝光(活化能射線之照射),曝光部(經活化能射線所照射之部分)會硬化。且,藉由接觸式(或非接觸方式),通過形成圖型之光罩,並選擇性地由活化能射線來曝光或由雷射直接曝光機來直接圖型 曝光後,將未曝光部以稀鹼水溶液(例如0.3~3質量%碳酸鈉水溶液)顯像來形成光阻圖型。 By exposing the coating film obtained by applying the photosensitive resin composition of the present invention and volatilizing a dry solvent (irradiation with active energy rays), the exposed portion (the portion irradiated with active energy rays) is hardened. And, by contact (or non-contact), by forming a mask of the pattern, and selectively exposing by active energy rays or direct patterning by a laser direct exposure machine After the exposure, the unexposed portion is developed with a dilute alkali aqueous solution (for example, a 0.3 to 3% by mass sodium carbonate aqueous solution) to form a photoresist pattern.
作為上述活化能射線照射所使用之曝光機,只要是裝載有高壓水銀燈管、超高壓水銀燈管、金屬鹵化物燈、水銀短弧燈等,並照射350~450nm之範圍的紫外線之裝置即可,也能夠進一步使用直接描畫裝置(例如由來自電腦的CAD數據以直接雷射描繪畫像的雷射直接影像裝置)。作為直描機之雷射光源,只要是使用最大波長在350~410nm之範圍的雷射光,無論是氣體雷射或固體雷射皆可。用於畫像形成的曝光量會因膜厚等而異,但一般來說能夠設在10~100mJ/cm2,較佳為20~800mJ/cm2之範圍內。 As the exposure machine used for the activation energy ray irradiation, any device that is equipped with a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a mercury short-arc lamp, and the like, and irradiates ultraviolet rays in the range of 350 to 450 nm, It is also possible to further use a direct drawing device (for example, a laser direct imaging device that draws an image with a direct laser from CAD data from a computer). As the laser light source of the direct scan machine, as long as it uses laser light with a maximum wavelength in the range of 350 to 410 nm, it can be a gas laser or a solid laser. The exposure amount used for image formation varies depending on the film thickness and the like, but can generally be set in the range of 10 to 100 mJ / cm 2 , preferably 20 to 800 mJ / cm 2 .
作為上述顯像方法,能夠藉由浸泡法、噴水法、噴霧法、刷拭法等,作為顯像液,能夠使用氫氧化鉀、氫氧化鈉、碳酸鈉、碳酸鉀、磷酸鈉、矽酸鈉、氨、胺類等之鹼水溶液。 As the developing method, a dipping method, a water spray method, a spray method, a brush method, or the like can be used. As the developing solution, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, Aqueous alkali solution of ammonia, amines, etc.
以下示出實施例以及比較例針對本發明進行具體說明,但本發明並不限定於下述實施例中。且,以下,「份」以及「%」意指只要沒有特別例外下之質量基準。 Examples and comparative examples are described below to specifically describe the present invention, but the present invention is not limited to the following examples. In the following, "parts" and "%" mean quality standards as long as there are no special exceptions.
在具備攪拌裝置、溫度計、冷凝器之反應容器中,置入由1,5-戊烷二醇與1,6-己二醇所衍生之聚碳酸酯二醇(Asahi-Kasei公司製,T5650J,數平均分子量800)2400g(3莫耳)、二羥甲基丙酸603g(4.5莫耳)以及作為單羥基化合物之2-羥乙基丙烯酸酯238g(2.6莫耳)。接著,置入作為聚異氰酸酯之異佛酮二異氰酸酯1887g(8.5莫耳),一邊攪拌一邊加熱至60℃,停止後,在反應容器內的溫度開始降低的時點再度加熱,於80℃下繼續攪拌,確認到紅外線吸收光譜中的異氰酸酯基之吸收光譜(2280cm-1)消失後,反應停止。添加卡必醇乙酸酯使固體成分成為70質量%。所得之含有羧基之樹脂的固體成分之酸價為50mgKOH/g。以下,將所得之清漆稱作含有羧基之樹脂溶液A-1。 In a reaction vessel equipped with a stirring device, a thermometer, and a condenser, a polycarbonate diol (manufactured by Asahi-Kasei, T5650J, derived from 1,5-pentanediol and 1,6-hexanediol) was placed. Number average molecular weight 800) 2400 g (3 moles), 603 g (4.5 moles) of dimethylolpropionic acid, and 238 g (2.6 moles) of 2-hydroxyethyl acrylate as a monohydroxy compound. Next, 1887 g (8.5 moles) of isophorone diisocyanate as a polyisocyanate was placed, and heated to 60 ° C while stirring. After stopping, heating was resumed when the temperature in the reaction vessel began to decrease, and the stirring was continued at 80 ° C. After confirming that the absorption spectrum (2280 cm -1 ) of the isocyanate group in the infrared absorption spectrum disappeared, the reaction stopped. Carbitol acetate was added to make the solid content 70% by mass. The acid value of the solid content of the obtained carboxyl group-containing resin was 50 mgKOH / g. Hereinafter, the obtained varnish is referred to as a carboxyl group-containing resin solution A-1.
將下述表1所示之成分以表中所示之比例(質量份)摻混,以攪拌機預備混合後,以3根滾筒碾磨機混練,調製感光性樹脂組成物。於此所得之各感光性樹脂組成物的分散度以Erichsen公司製Grind Meter的粒度測定來評估後,為15μm以下。 The ingredients shown in Table 1 below were blended in the proportions (parts by mass) shown in the table, pre-mixed with a blender, and kneaded with three roller mills to prepare a photosensitive resin composition. The dispersion of each of the photosensitive resin compositions obtained here was evaluated by a particle size measurement of a Grind Meter manufactured by Erichsen, and was 15 μm or less.
*1:ZFR-1401H(日本化藥公司製;固體成分量65%) * 1: ZFR-1401H (manufactured by Nippon Kayaku Co., Ltd .; solid content 65%)
*2:UN-3320HA(根上工業公司製;6官能之氨基甲酸乙酯丙烯酸酯) * 2: UN-3320HA (manufactured by Genjo Industrial Co., Ltd .; 6-functional urethane acrylate)
*3:UN-904(根上工業公司製;10官能之氨基甲酸乙酯丙 烯酸酯) * 3: UN-904 (manufactured by Gensang Kogyo; 10-functional urethane propylene Enoate)
*4:UN-3320HSBA(根上工業公司製;15官能之氨基甲酸乙酯丙烯酸酯) * 4: UN-3320HSBA (manufactured by Gensang Kogyo; 15-functional urethane acrylate)
*5:UN-952(根上工業公司製;10官能之氨基甲酸乙酯丙烯酸酯) * 5: UN-952 (manufactured by Genjo Industrial Co., Ltd .; 10-functional urethane acrylate)
*6:UN-905(根上工業公司製;15官能之氨基甲酸乙酯丙烯酸酯) * 6: UN-905 (manufactured by Gensang Kogyo; 15-functional urethane acrylate)
*7:EBECRYL8405(daicel-allnex公司製;4官能之氨基甲酸乙酯丙烯酸酯) * 7: EBECRYL8405 (manufactured by Daicel-Allnex Corporation; 4-functional urethane acrylate)
*8:Larmer LR8863(BASF Japan公司製;聚醚改質丙烯酸酯寡聚物) * 8: Larmer LR8863 (manufactured by BASF Japan; polyether modified acrylate oligomer)
*9:LUCIRIN TPO(BASF Japan公司製;醯基膦氧化物系光聚合起始劑) * 9: LUCIRIN TPO (manufactured by BASF Japan; fluorenylphosphine oxide-based photopolymerization initiator)
*10:IRGACURE-OXE-02(BASF Japan公司製;肟酯系光聚合起始劑) * 10: IRGACURE-OXE-02 (manufactured by BASF Japan; oxime ester photopolymerization initiator)
*11:Tipaque CR-97(石原產業公司製;金紅石型氧化鈦) * 11: Tipaque CR-97 (manufactured by Ishihara Industries; rutile titanium oxide)
*12:酞花青藍 * 12: Phthalocyanine blue
*13:HFA-6065E(昭和電工公司製) * 13: HFA-6065E (manufactured by Showa Denko Corporation)
*14:Exolit OP935(Clariant公司製)(平均粒徑:2~3μm) * 14: Exolit OP935 (manufactured by Clariant) (average particle size: 2 to 3 μm)
*15:Higilite H-42M(昭和電工公司製)(平均粒徑:1μm) * 15: Higilite H-42M (manufactured by Showa Denko Corporation) (average particle size: 1 μm)
*16:NC-3000H(日本化藥公司製) * 16: NC-3000H (manufactured by Nippon Kayaku Co., Ltd.)
*17:YX-4000(三菱化學公司製) * 17: YX-4000 (manufactured by Mitsubishi Chemical Corporation)
*18:KS-66(信越化學工業公司製) * 18: KS-66 (by Shin-Etsu Chemical Industry Co., Ltd.)
*19:Disperbyk-111(BYK.Japan公司製) * 19: Disperbyk-111 (by BYK. Japan)
*20:三聚氰胺粉碎品 * 20: crushed melamine
*21:Aerosil#974(EPOCH公司製) * 21: Aerosil # 974 (manufactured by EPOCH)
*22:DOWANOL DPM(Dow Chemical公司製) * 22: DOWANOL DPM (manufactured by Dow Chemical)
氨基甲酸乙酯丙烯酸酯之重量平均分子量是由GPC法(透膠層析術)並以標準聚苯乙烯換算所求得。測定條件表示於以下。 The weight average molecular weight of urethane acrylate is calculated | required by GPC method (permeation chromatography) by standard polystyrene conversion. The measurement conditions are shown below.
裝置:Waters 2695 Installation: Waters 2695
管柱:Waters HPSgel HR MB-L(6.0mm×15cm)2根 以及Waters HPSgel HR 1.0(6.0mm×15cm)2根 Water column: Waters HPSgel HR MB-L (6.0mm × 15cm) 2 And 2 Waters HPSgel HR 1.0 (6.0mm × 15cm)
樣品稀釋方法:0.5質量%四氫呋喃稀釋 Sample dilution method: 0.5% by mass of tetrahydrofuran
溶媒:四氫呋喃 Solvent: Tetrahydrofuran
性能評估: Performance evaluation:
將各實施例以及比較例之組成物以網印全面塗布於1.6mm銅固體FR-4基板上使乾燥膜厚成為20μm,於80℃下乾燥30分鐘後冷卻至室溫。之後,使用裝載有超高壓水銀燈(短弧燈5KW)之觸點斷開曝光裝置,以最適當的曝光量進行全面曝光,並將30℃之1質量%Na2CO3水溶液以噴霧壓0.2MPa之條件下進行顯像120秒,於150℃下進行熱硬化60分鐘,得到形成硬化塗膜的評估樣品。在所得之評估樣品上乘載在18μm的聚亞醯胺薄膜的兩面有貼附35μm的銅箔之基板(兩面銅包覆彈性基板),進一 步在其上方乘載直徑為12mm之圓形且底面平滑的1kg重物。在此狀態之下,將兩面銅包覆彈性基板平行地拉開約10cm,塗膜上是否有黑色痕由以下之基準來評估。 The composition of each Example and Comparative Example was screen-coated on a 1.6 mm copper solid FR-4 substrate so as to have a dry film thickness of 20 μm, dried at 80 ° C. for 30 minutes, and then cooled to room temperature. After that, the exposure device was opened using a contact equipped with an ultra-high pressure mercury lamp (short-arc lamp 5KW), and full exposure was performed at the most appropriate exposure amount. A 1% by mass Na 2 CO 3 aqueous solution at 30 ° C. was sprayed at 0.2 MPa. Under the conditions, development was performed for 120 seconds, and heat curing was performed at 150 ° C for 60 minutes to obtain an evaluation sample for forming a cured coating film. On the obtained evaluation sample, a substrate with a copper foil of 35 μm (both sides of a copper-clad elastic substrate) attached to both sides of an 18 μm polyurethane film was loaded, and a circle with a diameter of 12 mm was further loaded on the substrate and the bottom surface was smooth. 1kg weight. In this state, the copper-coated elastic substrate on both sides was pulled apart approximately 10 cm in parallel, and the presence or absence of black marks on the coating film was evaluated by the following criteria.
○:無黑色痕 ○: No black marks
△:存在幅度1mm以下的黑色痕 △: There are black marks with a width of 1 mm or less
×:存在幅度超過1mm的黑色痕或幅度為1mm以下的複數黑色痕 ×: There are black marks with a width exceeding 1 mm or plural black marks with a width of 1 mm or less
將各實施例以及比較例之組成物以網印全面塗布於1.6mm厚度的銅固體FR-4基板上,以80℃下乾燥30分鐘,並冷卻至室溫。之後,使用裝載有超高壓水銀燈(短弧燈5KW)之觸點斷開曝光裝置,以最適當的曝光量進行全面曝光,將30℃之1質量%Na2CO3水溶液以噴霧壓0.2MPa之條件下進行顯像120秒,於150℃下進行熱硬化60分鐘,得到形成硬化塗膜的評估樣品。針對所得之評估樣品,將塗膜表面以分光測色計(CM-2600d,Konicaminolta公司製)測定在360~740nm下的反射率(%)。 The composition of each Example and Comparative Example was screen-coated on a copper solid FR-4 substrate with a thickness of 1.6 mm, dried at 80 ° C. for 30 minutes, and cooled to room temperature. After that, use a contact opening exposure device equipped with an ultra-high pressure mercury lamp (short arc lamp 5KW) to perform full exposure at the most appropriate exposure amount. A 1% by mass Na 2 CO 3 aqueous solution at 30 ° C is sprayed at a pressure of 0.2 MPa. Development was performed under conditions for 120 seconds, and heat curing was performed at 150 ° C. for 60 minutes to obtain an evaluation sample for forming a cured coating film. With respect to the obtained evaluation sample, the reflectance (%) of the coating film surface at 360 to 740 nm was measured with a spectrophotometer (CM-2600d, manufactured by Konicaminolta).
將各實施例以及比較例之組成物以網印全面塗布於1.6mm厚之銅固體FR-4基板上使乾燥膜厚成為20μm,於80℃下乾燥30分鐘並冷卻至室溫。對此基板使用有裝載 超高壓水銀燈(短弧燈5KW)之觸點斷開曝光裝置,以最適當的曝光量並使用遮光部分的線幅度為100μm之負圖型進行曝光,將30℃之1質量%Na2CO3水溶液以噴霧壓0.2MPa之條件下進行顯像120秒,於150℃下進行熱硬化60分鐘作為評估樣品。將所得之評估樣品所移除的線幅度以光學顯微鏡測量,並由以下之評估基準來評估。 The composition of each example and comparative example was screen-coated on a copper solid FR-4 substrate with a thickness of 1.6 mm so as to have a dry film thickness of 20 μm, dried at 80 ° C. for 30 minutes, and cooled to room temperature. For this substrate, a contact opening exposure device equipped with an ultra-high-pressure mercury lamp (short-arc lamp 5KW) was used for exposure at the most appropriate exposure amount and using a negative pattern with a line width of 100 μm in the light-shielding portion. A mass% Na 2 CO 3 aqueous solution was developed under the condition of a spray pressure of 0.2 MPa for 120 seconds, and heat-cured at 150 ° C. for 60 minutes as an evaluation sample. The line width removed by the obtained evaluation sample was measured with an optical microscope and evaluated by the following evaluation criteria.
○:移除之線幅度為70μm以上 ○: The width of the removed line is 70 μm or more
△:移除之線幅度為50μm以上 △: The width of the removed line is 50 μm or more
×:移除之線幅度未滿50μm ×: The width of the removed line is less than 50 μm
將各實施例以及比較例之組成物以網印全面塗布於1.6mm厚之銅固體FR-4基板上,於80℃下乾燥30分鐘並冷卻至室溫。之後,使用裝載有超高壓水銀燈(短弧燈5KW)的觸點斷開曝光裝置,以最適當的曝光量進行全面曝光,將30℃之1質量%Na2CO3水溶液以噴霧壓0.2MPa之條件下進行顯像120秒,於150℃下進行熱硬化60分鐘,得到形成硬化塗膜之評估樣品。針對所得之評估樣品,使用micro-TRI-gloss(BYK.Japan公司製),測定60度鏡面反射率。 The compositions of each example and comparative example were screen-coated on a 1.6 mm thick copper solid FR-4 substrate, dried at 80 ° C. for 30 minutes, and cooled to room temperature. After that, using a contact opening exposure device equipped with an ultra-high pressure mercury lamp (short arc lamp 5KW), full exposure was performed at the most appropriate exposure amount, and a 1% by mass Na 2 CO 3 aqueous solution at 30 ° C. was sprayed at a pressure of 0.2 MPa. Development was performed under conditions for 120 seconds, and heat curing was performed at 150 ° C. for 60 minutes to obtain an evaluation sample for forming a hardened coating film. About the obtained evaluation sample, 60-degree specular reflectance was measured using micro-TRI-gloss (made by BYK. Japan).
將各實施例以及比較例之組成物以網印全面塗布於25μm厚之聚亞醯胺薄膜(Kapton 100H)上,於80℃下乾燥 20分鐘並冷卻至室溫。進一步對內面同樣地以網印進行全面塗布,於80℃下乾燥20分鐘並冷卻至室溫,得到兩面塗布基板。於此基板上使用裝載金屬鹵化物燈之曝光裝置(HMW-680-GW20),以最適當的曝光量將阻焊全面曝光,將30℃之1質量%Na2CO3水溶液以噴霧壓0.2MPa之條件下進行顯像120秒,於150℃下進行熱硬化60分鐘,作為評估樣品。針對此難燃性評估用樣品,進行以UL94規格為根據的薄材垂直燃燒試驗。評估是針對UL94規格,表示成VTM-0或VTM-1。 The composition of each example and comparative example was screen-coated on a 25 μm-thick polyurethane film (Kapton 100H), dried at 80 ° C. for 20 minutes, and cooled to room temperature. Further, the inner surface was completely coated with screen printing in the same manner, dried at 80 ° C. for 20 minutes, and cooled to room temperature to obtain a double-sided coated substrate. On this substrate, an exposure device (HMW-680-GW20) equipped with a metal halide lamp was used to fully expose the solder resist at the most appropriate exposure amount. A 1% by weight Na 2 CO 3 aqueous solution at 30 ° C was sprayed at a pressure of 0.2 MPa. Under the conditions, development was performed for 120 seconds, and heat curing was performed at 150 ° C for 60 minutes, which were used as evaluation samples. The flame retardant evaluation sample was subjected to a thin material vertical combustion test based on the UL94 standard. The evaluation is for the UL94 specification and is expressed as VTM-0 or VTM-1.
將各實施例以及比較例之組成物以網印全面塗布於25μm厚之聚亞醯胺薄膜(TORAY.Du Pont公司製Kapton 100H)上,於80℃下乾燥30分鐘並冷卻至室溫。之後,使用裝載有超高壓水銀燈(短弧燈5KW)之觸點斷開曝光裝置,以最適當的曝光量進行全面曝光,將30℃之1質量%Na2CO3水溶液以噴霧壓0.2MPa之條件下進行顯像120秒,於150℃下進行熱硬化60分鐘,得到形成有硬化塗膜之評估樣品。針對所得之評估樣品,使其具有R=0.8mm之間隙後,進行180°之折疊1次,目測以及以光學顯微鏡(倍率×200)觀察此時硬化塗膜中的破裂發生狀況,並由以下之評估基準來進行評估。 The composition of each example and comparative example was screen-coated on a 25 μm-thick polyimide film (Kapton 100H manufactured by TORAY. Du Pont), dried at 80 ° C. for 30 minutes, and cooled to room temperature. After that, use a contact opening exposure device equipped with an ultra-high pressure mercury lamp (short arc lamp 5KW) to perform full exposure at the most appropriate exposure amount. A 1% by mass Na 2 CO 3 aqueous solution at 30 ° C is sprayed at a pressure of 0.2 MPa. Development was performed under conditions for 120 seconds, and heat curing was performed at 150 ° C. for 60 minutes to obtain an evaluation sample with a cured coating film formed. For the obtained evaluation sample, after having a gap of R = 0.8mm, it was folded once at 180 °, and the occurrence of cracks in the hardened coating film at this time was visually observed and observed with an optical microscope (magnification × 200). Assessment basis.
○:即使折疊3次也不會發生破裂 ○: No breakage even when folded three times
△:1次沒有發生破裂,但是折疊2次至3次時發生破裂 △: No crack occurred once, but crack occurred when folded 2 to 3 times
×:折疊1次時發生破裂 ×: Rupture occurred when folded once
將實施例以及比較例之組成物使用IPC B-25之梳型電極B試片,以網印進行全面塗布,於80℃下乾燥30分鐘並冷卻至室溫。之後,使用裝載有超高壓水銀燈(短弧燈5KW)之觸點斷開曝光裝置,並以最適當的曝光量全面曝光,將30℃之1質量%Na2CO3水溶液以噴霧壓0.2MPa之條件下進行顯像120秒,於150℃下進行熱硬化60分鐘,得到評估樣品。對此梳型電極施加DC100V之偏電壓,確認85℃,85%R.H.之恆溫恆濕槽在1,000小時後的位移之有無,由以下之評估基準來評估。 The composition of the examples and comparative examples was coated with a comb-shaped electrode B test piece of IPC B-25 by screen printing, and dried at 80 ° C. for 30 minutes and cooled to room temperature. After that, the exposure device was opened using a contact equipped with an ultra-high pressure mercury lamp (short arc lamp 5KW), and full exposure was performed at the most appropriate exposure amount. A 1% by mass Na 2 CO 3 aqueous solution at 30 ° C was sprayed at a pressure of 0.2 MPa. Development was performed under the conditions for 120 seconds, and heat curing was performed at 150 ° C for 60 minutes to obtain an evaluation sample. A bias voltage of 100 V DC was applied to the comb electrode, and the presence or absence of displacement of the constant temperature and humidity bath at 85 ° C and 85% RH after 1,000 hours was confirmed by the following evaluation criteria.
○:認為完全沒有變化 ○: No change at all
△:僅有變化 △: Only change
×:位移發生 ×: displacement occurs
*32:重量平均分子量4,900且官能基數10之氨基甲酸乙酯丙烯酸酯與重量平均分子量50,000且官能基數15之氨基甲酸乙酯丙烯酸酯 * 32: Urethane acrylate with a weight average molecular weight of 4,900 and 10 functional groups and urethane acrylate with a weight average molecular weight of 50,000 and 15 functional groups
由上述表1、2所示之結果可得知,為實施例之感光性樹脂組成物時,硬化物上較難以產生磨擦痕跡。另一方面,不含有(B)官能基數為6個以上的氨基甲酸乙酯(甲基)丙烯酸酯的比較例1、2,其硬化物上容易產生磨擦痕跡。 From the results shown in Tables 1 and 2 above, it can be seen that in the case of the photosensitive resin composition of the example, it is difficult to produce friction marks on the cured product. On the other hand, in Comparative Examples 1 and 2 which did not contain a urethane (meth) acrylate having 6 or more (B) functional groups, frictional marks were easily generated on the cured product.
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