JP2014059505A - Alkali-soluble resin composition, cured product thereof, and optical waveguide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an alkali-soluble resin composition which is soluble in alkali, rapidly cures by being irradiated with active energy rays (in particular, light), and is capable of forming a cured product having all of heat resistance, flexibility, and transparency.SOLUTION: The alkali-soluble resin composition contains: a cationically curable polymer (A) which is a radical copolymer of monomer components containing an oxetane ring-containing (meth)acryloyl compound (a1) having a specific structure and a radically polymerizable compound (a2) having an alkali-soluble group in the molecule; an alkali-soluble cationically polymerizable compound (B) other than the cationically curable polymer (A); and a cationic polymerization initiator (C). The alkali-soluble resin composition has an acid value of 40-200 mgKOH/g.

Description

  The present invention relates to an alkali-soluble resin composition, a cured product thereof, and an optical waveguide. Specifically, it is a cationic curable resin that is soluble in an alkali and that cures quickly by irradiation with active energy rays (particularly light) to form a cured product having excellent flexibility, transparency, and heat resistance. The present invention relates to a composition, a cured product thereof, and an optical waveguide (polymer optical waveguide) produced using the resin composition.

  In recent years, in order to cope with an increase in the capacity of information, research on high-speed CPU processing has been actively conducted. However, because there are concerns about malfunctions due to noise generation and adverse effects due to electromagnetic waves in existing conductive wiring, a part of the copper electrical wiring on the printed circuit board is replaced with optical fiber or optical waveguide optical wiring instead of electrical signals. Attempts have been made to use optical signals.

  The optical waveguide used as the above-mentioned optical wiring is mainly manufactured by a photolithography method. Specifically, for example, a photo-curable resin composition is applied on a substrate, irradiated with light through a photomask, and an unmasked portion is selectively polymerized, and then an unexposed portion of light (light By removing the uncured portion of the curable resin composition using a solvent or the like, an optical waveguide pattern (for example, a core pattern) is formed. In such a method, there is a development step for washing away the uncured part of the photocurable resin composition, but as a developer, an organic solvent is generally used, and the environmental burden, harmfulness to the human body, There were problems such as fire hazard. In order to avoid such a problem, a developing method using an alkaline aqueous solution as a developer instead of an organic solvent is also performed.

  On the other hand, the required characteristics for optical wiring include heat resistance that can withstand solder reflow, flexibility to accommodate downsizing in short-distance transmission equipment such as mobile phones, and transparency to achieve low optical loss. Etc. However, a resin composition that can correspond to a photolithography method using an aqueous alkali solution as a developer (that is, has alkali solubility) and can form a material (cured product) having heat resistance, flexibility, and transparency (cured product) ( The present situation is that a photocurable resin composition) has not yet been found. For example, Patent Document 1 discloses a positive radiation-sensitive composition containing a specific alkali-soluble copolymer, a 1,2-quinonediazide compound, and a water-repellent siloxane resin in a specific ratio. The cured product of the radiation-sensitive composition was colored by thermal decomposition, and had a problem that the light transmittance in the visible light region was lowered. Further, Patent Document 2 discloses a low optical loss and high heat resistance optical waveguide material using polyimides having high heat resistance. However, the material has a problem that flexibility is insufficient. It was.

JP 2004-4733 A JP-A-6-265738

Therefore, an object of the present invention is to cure which is soluble in alkali and is rapidly cured by irradiation with an active energy ray (particularly light), and has heat resistance, flexibility and transparency. An object is to provide an alkali-soluble resin composition capable of forming a product.
Moreover, the other object of this invention is to provide the hardened | cured material which has heat resistance, a softness | flexibility, and transparency.
Furthermore, another object of the present invention is to provide an optical waveguide which can be formed by a developing method using an alkaline aqueous solution and has excellent heat resistance and flexibility with low light loss.

  As a result of intensive studies to solve the above problems, the present inventors have found that a cationically curable polymer obtained by radical copolymerization of a specific combination of monomers, a cationically polymerizable compound having alkali solubility, and initiation of polymerization. And a resin composition having a specific acid value is soluble in alkali and quickly cured by irradiation with active energy rays (especially light), heat resistance, flexibility And it discovered that the hardened | cured material which had transparency could be formed, and completed this invention.

［式（１）中、Ｒ¹、Ｒ²は同一又は異なって水素原子又はアルキル基を示す。Ａは炭素数２〜２０の直鎖又は分岐鎖状のアルキレン基を示す。］
で表されるオキセタン環含有（メタ）アクリロイル化合物（ａ１）及び分子内にアルカリ可溶性基を有するラジカル重合性化合物（ａ２）を含む単量体成分のラジカル共重合体であるカチオン硬化性重合物（Ａ）と、該カチオン硬化性重合物（Ａ）以外のアルカリ可溶性カチオン重合性化合物（Ｂ）と、カチオン重合開始剤（Ｃ）とを含み、酸価が４０〜２００ｍｇＫＯＨ／ｇであることを特徴とするアルカリ可溶型樹脂組成物を提供する。 That is, the present invention provides the following formula (1):

[In Formula (1), R < ¹ >, R < ² > is the same or different and shows a hydrogen atom or an alkyl group. A represents a linear or branched alkylene group having 2 to 20 carbon atoms. ]
A cationically curable polymer that is a radical copolymer of a monomer component containing an oxetane ring-containing (meth) acryloyl compound (a1) and a radically polymerizable compound (a2) having an alkali-soluble group in the molecule ( A), an alkali-soluble cationic polymerizable compound (B) other than the cationic curable polymer (A), and a cationic polymerization initiator (C), wherein the acid value is 40 to 200 mgKOH / g An alkali-soluble resin composition is provided.

Furthermore, the cationic curable polymer (A) is an oxetane ring-containing (meth) acryloyl compound (a1), a radically polymerizable compound (a2) having an alkali-soluble group in the molecule, and (a1) and (a2) A radical copolymer of a monomer component containing the radical polymerizable compound (a3):
The radical polymerizable compound (a3) is selected from the group consisting of (meth) acryloyl group, (meth) acryloyloxy group, (meth) acryloylamino group, vinylaryl group, vinyl ether group, and vinyloxycarbonyl group. The alkali-soluble resin composition is a compound having only one group in the molecule.

  Further, the ratio of the cation curable polymer (A) to the alkali-soluble cation polymerizable compound (B) [cation curable polymer (A) / alkali-soluble cation polymerizable compound (B)] (weight ratio) is 85 / The alkali-soluble resin composition is 15 to 45/55.

  Furthermore, the above alkali-soluble resin composition, which is a resin composition for optical waveguide materials, is provided.

  Moreover, this invention provides the hardened | cured material obtained by hardening the said alkali-soluble resin composition by active energy ray irradiation and a heating.

  Moreover, this invention provides the optical waveguide containing the said hardened | cured material.

  Since the alkali-soluble resin composition of the present invention has the above-described configuration, it is soluble in alkali, and is rapidly cured (cationic curing) by irradiation with active energy rays (particularly light). A cured product having heat resistance, flexibility, and transparency can be formed. For this reason, when the alkali-soluble resin composition of the present invention is used, an optical waveguide can be produced by a photolithography method including a development process using an aqueous alkali solution. By adopting such a manufacturing method, it is possible to avoid problems such as environmental load, harmfulness to human body, fire risk, etc. due to the use of organic solvents. Moreover, the optical waveguide manufactured using the alkali-soluble resin composition of the present invention has low light loss, and is excellent in heat resistance and flexibility.

Change in weight of cured product in thermogravimetric analysis (vertical axis: weight ratio (%) when weight before heating is 100%, horizontal axis: temperature (° C)), and thermal decomposition temperature (T It is a figure which shows the method of calculating. It is the schematic (sectional drawing) which shows the manufacturing method of an optical waveguide.

The alkali-soluble resin composition of the present invention includes a cationic curing polymer (A) described below, an alkali-soluble cationic polymerizable compound (B) described below, and a cationic polymerization initiator (C) as essential components. It is an adhesive resin composition.
Cationic curable polymer (A): an oxetane ring-containing (meth) acryloyl compound represented by the following formula (1) (sometimes simply referred to as “oxetane ring-containing (meth) acryloyl compound (a1)”), and , A radical copolymer of a monomer component containing at least a radical polymerizable compound having an alkali-soluble group in the molecule (sometimes simply referred to as “radical polymerizable compound (a2)”).
Alkali-soluble cationically polymerizable compound (B): A compound other than the cationically curable polymer (A), which is soluble in alkali.

The alkali-soluble resin composition of the present invention is a resin composition that is soluble in alkali. Specifically, in this specification, “soluble in alkali” means soluble in 1% aqueous sodium hydrogen carbonate solution, more specifically, 1% hydrogen carbonate. The solubility in an aqueous sodium solution (solubility at 23 ° C.) is preferably 10% [g / 100 g-1% NaHCO ₃ aq] or more (for example, 10 to 100%), more preferably 15% or more, and further preferably 20% or more. is there.

  The acid value of the alkali-soluble resin composition of the present invention is 40 to 200 mgKOH / g, preferably 45 to 120 mgKOH / g. When the acid value is less than 40 mgKOH / g, development using an aqueous alkali solution (alkali development) may be difficult in photolithography. On the other hand, when the acid value exceeds 200 mgKOH / g, the exposed portion is dissolved by an alkaline aqueous solution (developer) in photolithography, so that the line becomes thinner than necessary, and in some cases, the exposed portion and the unexposed portion It is not preferable because it is dissolved and peeled off with a developer without distinction, and drawing becomes difficult. In addition, the acid value of the alkali-soluble resin composition of the present invention can be measured according to JIS K0070.

[Cation curable polymer (A)]
As described above, the cationic curable polymer (A) in the alkali-soluble resin composition of the present invention contains the oxetane ring-containing (meth) acryloyl compound (a1) and the radical polymerizable compound (a2) as essential components. It is a radical copolymer (radical copolymer) of a monomer component. The monomer component constituting the cationic curable polymer (A) includes a radical polymerizable compound other than the oxetane ring-containing (meth) acryloyl compound (a1) and the radical polymerizable compound (a2) (“radical polymerizable compound ( a3) ”may be included). That is, the monomer component constituting the cationic curable polymer (A) is a mixture of the oxetane ring-containing (meth) acryloyl compound (a1) and the radical polymerizable compound (a2), or the oxetane ring-containing (meth) acryloyl. It is a mixture of the compound (a1), the radical polymerizable compound (a2), and the radical polymerizable compound (a3).

  In other words, the cationic curable polymer (A) is a structural unit derived from the oxetane ring-containing (meth) acryloyl compound (a1) (repeating structural unit; structural unit represented by the formula (i) described later) and radical polymerization. It is a radical copolymer which has a structural unit (repeating structural unit) derived from an ionic compound (a2) as an essential structural unit. The cationic curable polymer (A) may further have a structural unit (repeating structural unit) derived from the radical polymerizable compound (a3).

  The cationic curable polymer (A) may be a block copolymer or a random copolymer.

(Oxetane ring-containing (meth) acryloyl compound (a1))
The oxetane ring-containing (meth) acryloyl compound (a1), which is an essential monomer component of the cationic curable polymer (A), is cationically polymerized in the molecule (in one molecule) as shown in the above formula (1). It is a compound having an oxetane ring (oxetanyl group) as a site and a CH ₂ ═CR ¹ CO— group (particularly an acryloyl group or a methacryloyl group) as a radical polymerization site. In the present specification, “(meth) acryloyl” means either one or both of an acryloyl group and a methacryloyl group. However, “(meth) acryloyl” in the oxetane ring-containing (meth) acryloyl compound includes not only an acryloyl group and a methacryloyl group but also a CH ₂ ═CR ¹ CO— group in which R ¹ is an alkyl group other than a methyl group. Shall be included.

In formula (1), R ¹ represents a hydrogen atom or an alkyl group. R ² represents a hydrogen atom or an alkyl group. R ¹ and R ² may be the same or different. As the alkyl group in R ¹ and R ^2, an alkyl group having 1 to 6 carbon atoms (C _1-6 ) is preferable, and examples thereof include straight groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. Chain C _1-6 (preferably C _1-3 ) alkyl group; isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, s-pentyl group, t-pentyl group, isohexyl group, Examples thereof include branched C _3-6 (preferably C ₃ ) alkyl groups such as s-hexyl group and t-hexyl group. Among them, R ¹ is preferably a hydrogen atom or a methyl group. R ² is preferably a methyl group or an ethyl group.

［式（ａ−１）中、ｎ１は２以上の整数を示す。式（ａ−２）中、Ｒ³、Ｒ⁴、Ｒ⁷、Ｒ⁸は同一又は異なって水素原子又はアルキル基を示し、Ｒ⁵、Ｒ⁶は同一又は異なってアルキル基を示す。ｎ２は０以上の整数を示し、ｎ２が２以上の整数の場合、２以上のＲ⁷、Ｒ⁸はそれぞれ同一であってもよく、異なっていてもよい。］ In the formula (1), A represents a linear or branched alkylene group having 2 to 20 carbon atoms. Especially, as said A, the linear alkylene group represented by following formula (a-1), or following formula (a-) by the point which can form the hardened | cured material which has the outstanding heat resistance and a softness | flexibility. The branched alkylene group represented by 2) is preferred. In addition, the right end of Formula (a-2) couple | bonds with the oxygen atom which comprises an ester bond.

[In Formula (a-1), n1 represents an integer of 2 or more. In formula (a-2), R ³ , R ⁴ , R ⁷ and R ⁸ are the same or different and represent a hydrogen atom or an alkyl group, and R ⁵ and R ⁶ are the same or different and represent an alkyl group. n2 represents an integer of 0 or more. When n2 is an integer of 2 or more, 2 or more of R ⁷ and R ⁸ may be the same or different. ]

  N1 in formula (a-1) represents an integer of 2 or more, and is not particularly limited, but is preferably an integer of 2 to 20, particularly preferably an integer of 2 to 10. When n1 is 1, the flexibility of the cured product obtained by polymerization tends to decrease.

As an alkyl group in R < ³ >, R < ⁴ >, R < ⁵ >, R < ⁶ >, R <^7> , R < ⁸ > in Formula (a-2), a C1-C4 alkyl group is preferable, for example, a methyl group, an ethyl group, Linear C _1-4 (preferably C _1-3 ) alkyl group such as propyl group and butyl group; branched chain C ₃₋ such as isopropyl group, isobutyl group, s-butyl group and t-butyl group ₄ (preferably C ₃ ) alkyl group and the like. Among these, hydrogen atoms are preferable as R ³ and R ⁴ . Moreover, as said R < ⁵ >, R < ⁶ >, a methyl group and an ethyl group are preferable.

  N2 in the formula (a-2) represents an integer of 0 or more, and is not particularly limited, but is preferably an integer of 1 to 20, particularly preferably an integer of 1 to 10.

Typical examples of the oxetane ring-containing (meth) acryloyl compound (a1) include the following compounds.

  As a monomer (monomer component) of the cationic curable polymer (A), the oxetane ring-containing (meth) acryloyl compound (a1) can be used alone or in combination of two or more. It can also be used.

  Content of the oxetane ring-containing (meth) acryloyl compound (a1) with respect to the total amount (100% by weight) of the monomer components constituting the cationic curable polymer (A) (the total amount of these when including two or more) Is not particularly limited, but is preferably 10 to 90% by weight, more preferably 15 to 70% by weight, and still more preferably 20 to 50% by weight. If the content is less than 10% by weight, the heat resistance of the cured product may be insufficient. On the other hand, when the content exceeds 90% by weight, the alkali solubility may be insufficient.

The cationic curable polymer (A) is a polymer containing at least a structural unit derived from an oxetane ring-containing (meth) acryloyl compound (a1), that is, a structural unit (repeating structural unit) represented by the following formula (i). It is. Since the cation curable polymer (A) has an oxetanyl group which is a cation polymerizable group in the side chain of the polymer as shown in the following formula (i), the cation curable polymer (A) has an excellent cation polymerizable (cation curable) weight. It is a coalescence (cationic curable resin).

［式（２）中、Ｒ²は前記に同じ。Ｘは脱離性基を示す。］
で表される化合物と、下記式（３）
ＨＯ−Ａ−ＯＨ （３）
［式（３）中、Ａは前記に同じ。］
で表される化合物を、塩基性物質の存在下、液相一相系で反応させて下記式（４）

［式（４）中、Ｒ²、Ａは前記に同じ。］
で表されるオキセタン環含有アルコールを得、得られたオキセタン環含有アルコールを（メタ）アクリル化することにより合成することができる。 The oxetane ring-containing (meth) acryloyl compound (a1) is, for example, represented by the following formula (2):

[In formula (2), R ² is the same as above. X represents a leaving group. ]
And a compound represented by the following formula (3)
HO-A-OH (3)
[In Formula (3), A is the same as the above. ]
A compound represented by the following formula (4) is reacted in a liquid phase one-phase system in the presence of a basic substance.

[In the formula (4), R ² and A are the same as above. ]
It can be synthesized by obtaining an oxetane ring-containing alcohol represented by the formula (1) and (meth) acrylating the obtained oxetane ring-containing alcohol.

  In formula (2), X represents a leaving group, for example, a halogen atom such as chlorine, bromine and iodine (among others, a bromine atom and an iodine atom are preferred); a p-toluenesulfonyloxy group, a methanesulfonyloxy group, Examples thereof include sulfonyloxy groups such as trifluoromethanesulfonyloxy group; and groups having high leaving properties such as acyloxy groups such as acetyloxy group.

Examples of the basic substance include alkali metal or alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide, calcium hydroxide, and magnesium hydroxide; sodium hydride, magnesium hydride, calcium hydride, and the like. Alkali metal or alkaline earth metal hydrides; alkali metal or alkaline earth metal carbonates such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate; organolithium reagents (eg, methyl lithium, ethyl lithium, n- butyl lithium, sec- butyl lithium, tert- butyl lithium, etc.), an organic magnesium reagent (Grignard reagent: for _{example, CH 3 MgBr, CH 3 CH} 2 MgBr or the like) an organic metal compound such as and the like. A basic substance can also be used individually by 1 type, and can also be used in combination of 2 or more type.

  The above “liquid phase single phase system” means a case where the liquid phase is not two or more but only one phase, and may contain a solid if the liquid phase is a single phase. The solvent constituting the one-phase liquid phase may be any solvent that can dissolve both the compound represented by the formula (2) and the compound represented by the formula (3). Aromatic hydrocarbons such as toluene, xylene and ethylbenzene; ethers such as THF (tetrahydrofuran) and IPE (isopropyl ether); sulfur-containing solvents such as DMSO (dimethyl sulfoxide); nitrogen-containing solvents such as DMF (dimethylformamide) Etc.

  The (meth) acrylation is, for example, a method in which (meth) acrylic acid or a derivative thereof (for example, (meth) acrylic acid chloride or the like) is reacted with an oxetane ring-containing alcohol represented by the formula (4). It can be carried out by a known or conventional method. The produced oxetane ring-containing (meth) acryloyl compound (a1) can be purified and isolated by a known or conventional method.

(Radically polymerizable compound (a2))
The radical polymerizable compound (a2) which is an essential monomer component of the cationic curable polymer (A) is a radical polymerizable compound having an alkali-soluble group in the molecule as described above. That is, the radically polymerizable compound (a2) is a compound having one or more alkali-soluble groups and one or more radically polymerizable groups in the molecule.

  Examples of the alkali-soluble group possessed by the radically polymerizable compound (a2) include groups (for example, acid groups and the like) that can impart properties that are soluble in an aqueous alkali solution (for example, a developer that is an aqueous alkali solution). Specifically, functional groups such as a carboxyl group, a phenolic hydroxyl group, a phosphoric acid group, a sulfonic acid group, a fluorinated alcohol group, a carboxylic acid anhydride group, and an active methylene group are exemplified. Of these, a carboxyl group and a phenolic hydroxyl group are preferable.

  The number of alkali-soluble groups in the molecule of the radical polymerizable compound (a2) may be one or more, and is not particularly limited, but is preferably 1 to 4, more preferably 1 to 3, and still more preferably. One or two, particularly preferably one.

  Examples of the radical polymerizable group possessed by the radical polymerizable compound (a2) include a group containing an ethylenically unsaturated double bond. Specific examples include a (meth) acryloyl group, a (meth) acryloyloxy group, Examples include (meth) acryloylamino group, vinyl ether group, vinylaryl group, vinyloxycarbonyl group and the like.

  The number of radical polymerizable groups in the molecule of the radical polymerizable compound (a2) may be one or more, and is not particularly limited, but is preferably 1 to 4, more preferably 1 to 3, and still more preferably. Is 1 or 2, particularly preferably 1.

  Specific examples of the radically polymerizable compound (a2) include unsaturated carboxylic acids, and more specifically, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and the like. Α, β-unsaturated carboxylic acid of 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl hexahydrophthalic acid, 2-methacryloyloxyethyl acid phosphate, hydroxystyrene and the like. Especially, as a radically polymerizable compound (a2), acrylic acid and methacrylic acid are especially preferable. In addition, the radically polymerizable compound (a2) can be used alone as a monomer component constituting the cationic curable polymer (A), or two or more kinds can be used in combination. .

  The content of the radically polymerizable compound (a2) with respect to the total amount (100% by weight) of the monomer component constituting the cationic curable polymer (A) (the total amount of these when two or more types are included) is particularly limited. However, it is preferably 10 to 45% by weight, more preferably 12 to 40% by weight, and still more preferably 15 to 35% by weight. If the content is less than 10% by weight, the resin composition may have insufficient alkali solubility (alkali solubility). On the other hand, if the content exceeds 45% by weight, the alkali solubility of the cured product becomes too high, and development using an aqueous alkali solution may be difficult.

(Radically polymerizable compound (a3))
As described above, the monomer component constituting the cationic curable polymer (A) is a radical polymerizable compound (a3) other than the oxetane ring-containing (meth) acryloyl compound (a1) and the radical polymerizable compound (a2). May be included. That is, the cationic curable polymer (A) is a radical copolymer of monomer components including an oxetane ring-containing (meth) acryloyl compound (a1), a radical polymerizable compound (a2), and a radical polymerizable compound (a3). It may be a coalescence.

  Examples of the radical polymerizable compound (a3) include compounds having one or more radical polymerizable groups in the molecule and having no alkali-soluble group. Specifically, for example, a compound having at least one (meth) acryloyl group in the molecule and not having an alkali-soluble group; having at least one (meth) acryloyloxy group in the molecule, and having an alkali-soluble group A compound having no one or more (meth) acryloylamino groups in the molecule and having no alkali-soluble group; a compound having one or more vinyl ether groups in the molecule and having no alkali-soluble group; And compounds having one or more vinylaryl groups and having no alkali-soluble group; compounds having one or more vinyloxycarbonyl groups in the molecule and having no alkali-soluble group.

  Examples of the compound having one or more (meth) acryloyl groups in the molecule and not having an alkali-soluble group include 1-buten-3-one, 1-penten-3-one, and 1-hexen-3-one. 4-phenyl-1-buten-3-one, 5-phenyl-1-penten-3-one, and derivatives thereof.

  Examples of the compound having one or more (meth) acryloyloxy groups in the molecule and not having an alkali-soluble group include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl ( (Meth) acrylate, t-butyl methacrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, n-lauryl (meth) acrylate, n-stearyl (meth) acrylate, n-butoxy Ethyl (meth) acrylate, butoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydro Rufuryl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) Acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1,4 -Butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonane Di (meth) acrylate, 1,10-decanediol di (meth) acrylate, decane di (meth) acrylate, glycerin di (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl (meth) acrylate, dimethylol tricyclode Candi (meth) acrylate, trifluoroethyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, isoamyl (meth) acrylate, isomyristyl (meth) acrylate, γ- (meth) acryloyloxypropyltrimethoxysilane, 2- (Meth) acryloyloxyethyl isocyanate, 1,1-bis (acryloyloxy) ethyl isocyanate, 2- (2-methacryloyloxyethyloxy) ethyl isocyanate, 3- (meth) acrylo Le trimethoxy silane, 2-methacryloyloxyethyl-2-hydroxypropyl phthalate, and derivatives thereof.

  Examples of the compound having one or more (meth) acryloylamino groups in the molecule and not having an alkali-soluble group include 4-acryloylmorpholine, N, N-dimethylacrylamide, N, N-diethylacrylamide, and N-methyl. Examples include acrylamide, N-ethylacrylamide, N-propylacrylamide, N-isopropylacrylamide, N-butylacrylamide, Nn-butoxymethylacrylamide, N-hexylacrylamide, N-octylacrylamide, and derivatives thereof.

  Examples of the compound having one or more vinyl ether groups in the molecule and not having an alkali-soluble group include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxyisopropyl vinyl ether, 4- Hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 2-hydroxybutyl vinyl ether, 3-hydroxyisobutyl vinyl ether, 2-hydroxyisobutyl vinyl ether, 1-methyl-3-hydroxypropyl vinyl ether, 1-methyl-2-hydroxypropyl vinyl ether, 1- Hydroxymethylpropyl vinyl ether, 4-hydroxycyclohexyl vinyl ether, 1,6-hexanediol monovinyl ether, 1 4-cyclohexanedimethanol monovinyl ether, 1,3-cyclohexanedimethanol monovinyl ether, 1,2-cyclohexanedimethanol monovinyl ether, p-xylene glycol monovinyl ether, m-xylene glycol monovinyl ether, o-xylene glycol monovinyl ether, diethylene glycol Monovinyl ether, triethylene glycol monovinyl ether, tetraethylene glycol monovinyl ether, pentaethylene glycol monovinyl ether, oligoethylene glycol monovinyl ether, polyethylene glycol monovinyl ether, dipropylene glycol monovinyl ether, tripropylene glycol monovinyl ether, tetrapropylene glycol monovinyl ether Ether, penta propylene glycol monomethyl ether, oligo propylene glycol monomethyl ether, polypropylene glycol monovinyl ether, and derivatives thereof.

  Examples of the compound having one or more vinylaryl groups in the molecule and not having an alkali-soluble group include styrene, divinylbenzene, methoxystyrene, ethoxystyrene, vinylnaphthalene, vinylanthracene, 4-vinylphenyl acetate, (4 -Vinylphenyl) dihydroxyborane, N- (4-vinylphenyl) maleimide and the like and derivatives thereof.

  Examples of the compound having one or more vinyloxycarbonyl groups in the molecule and not having an alkali-soluble group include, for example, isopropenyl formate, isopropenyl acetate, isopropenyl propionate, isopropenyl butyrate, isopropenyl isobutyrate, and caproic acid. Isopropenyl, isopropenyl valerate, isopropenyl isovalerate, isopropenyl lactate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprylate, vinyl laurate, vinyl myristate, vinyl palmitate, stearic acid Vinyl, vinyl cyclohexanecarboxylate, vinyl pivalate, vinyl octylate, vinyl monochloroacetate, divinyl adipate, vinyl methacrylate, vinyl crotrate, vinyl sorbate, vinyl benzoate, vinyl cinnamate, etc. Derivatives of al the like.

  As the radically polymerizable compound (a3), a (meth) acryloyl group, a (meth) acryloyloxy group, and a (meth) acryloylamino group are particularly preferable in that a cured product having excellent flexibility and heat resistance can be formed. , A compound having only one functional group (radical polymerizable group) selected from the group consisting of a vinylaryl group, a vinyl ether group, and a vinyloxycarbonyl group in the molecule is preferred, and in particular, a (meth) acryloyloxy group is present in the molecule. A compound having only one compound (for example, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl methacrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, etc.)), vinyl in the molecule Compounds having only one aryl group [eg styrene etc.] are preferredIn addition, a radically polymerizable compound (a3) can also be used individually by 1 type as a monomer of a cationic curable polymer (A), and can also be used in combination of 2 or more type.

  The content of the radically polymerizable compound (a3) with respect to the total amount (100% by weight) of the monomer component constituting the cation curable polymer (A) (the total amount of these when including two or more) is particularly limited. However, it is preferably 0 to 80% by weight, more preferably 20 to 75% by weight, and still more preferably 30 to 70% by weight. When content exceeds 80 weight%, the heat resistance of a hardened | cured material and a softness | flexibility may fall.

  The cation curable polymer (A) in the alkali-soluble resin composition of the present invention is a monomer component containing as essential components an oxetane ring-containing (meth) acryloyl compound (a1) and a radically polymerizable compound (a2) ( If necessary, it can be produced by radical polymerization (radical copolymerization) of a monomer component containing a radical polymerizable compound (a3).

  The radical polymerization (radical polymerization reaction) can proceed or be promoted by performing heat treatment and / or active energy ray (particularly, light) irradiation. When performing the heat treatment, the temperature can be appropriately adjusted according to the component used for the reaction, the type of the catalyst, and the like, and is not particularly limited, but is preferably 20 to 200 ° C, more preferably 50 to 150 ° C, More preferably, it is 70-120 degreeC. When active energy ray irradiation (particularly, light irradiation) is performed, as the light source, for example, a mercury lamp, a xenon lamp, a carbon arc lamp, a metal halide lamp, sunlight, an electron beam source, a laser light source, or the like can be used. . Moreover, after active energy ray irradiation (especially light irradiation), you may heat-process at the temperature of about 50-180 degreeC, for example, and may advance a radical polymerization reaction further. In addition, about the time (polymerization time) which advances the said radical polymerization, it can adjust suitably and is not specifically limited.

  The radical polymerization is generally performed in the presence of a solvent. As the solvent, known or conventional solvents can be used, and are not particularly limited, and examples thereof include 1-methoxy-2-acetoxypropane (PGMEA), benzene, toluene and the like. The radical polymerization may be performed in the absence of a solvent.

  In the radical polymerization, a radical polymerization initiator may be used. As the radical polymerization initiator, those capable of causing radical polymerization such as known or commonly used thermal radical polymerization initiators and photo radical polymerization initiators can be used, and are not particularly limited. For example, a radical polymerization initiator such as benzoyl peroxide can be used. Examples thereof include oxide polymerization initiators; azo polymerization initiators such as azobisisobutyronitrile (AIBN), azobis-2,4-dimethylvaleronitrile, and 2,2′-azobis (isobutyric acid) dimethyl.

  Although it does not specifically limit as the usage-amount of the radical polymerization initiator in the said radical polymerization, 0.01-50 weight part with respect to 100 weight part of whole quantity of the monomer component which comprises a cationic curable polymer (A). Is preferable, more preferably 0.05 to 20 parts by weight, still more preferably 0.1 to 18 parts by weight.

  The radical polymerization is preferably allowed to proceed in an inert gas atmosphere such as a nitrogen atmosphere or an argon atmosphere. Moreover, the radical polymerization can be allowed to proceed under normal pressure, or can be allowed to proceed under reduced pressure or under pressure.

  Although the weight average molecular weight of a cationic curable polymer (A) is not specifically limited, 500 or more (for example, 500-1 million) are preferable, More preferably, it is 3000-500,000. If the weight average molecular weight is outside the above range, the flexibility of a cured product obtained by curing the alkali-soluble resin composition tends to be difficult to obtain.

  The number average molecular weight of the cationic curable polymer (A) is not particularly limited, but is preferably 100 or more (for example, 100 to 500,000), more preferably 300 to 250,000. When the number average molecular weight is out of the above range, the flexibility of the cured product obtained by curing the alkali-soluble resin composition tends to be insufficient. In addition, the weight average molecular weight and number average molecular weight of a cationic curable polymer (A) can be measured as a value of standard polystyrene conversion by GPC (gel permeation chromatography) method, for example.

  Although the acid value of a cationic curable polymer (A) is not specifically limited, 40-200 mgKOH / g is preferable, More preferably, it is 45-120 mgKOH / g. When the acid value is less than 40 mgKOH / g, development using an aqueous alkali solution (alkali development) may be difficult in photolithography. On the other hand, when the acid value exceeds 200 mgKOH / g, the exposed portion is dissolved by an alkaline aqueous solution (developer) in photolithography, so that the line becomes thinner than necessary, and in some cases, the exposed portion and the unexposed portion It is not preferable because it is dissolved and peeled off with a developer without distinction, and drawing becomes difficult. The acid value of the cationic curable polymer (A) can be measured according to JIS K0070.

The cationic curable polymer (A) is preferably soluble in alkali (alkaline aqueous solution; for example, 1% sodium hydrogen carbonate aqueous solution). Specifically, the solubility (solubility at 23 ° C.) of the cationic curable polymer (A) in a 1% aqueous sodium hydrogen carbonate solution is not particularly limited, but is 10% [g / 100 g-1% NaHCO ₃ aq] or more ( For example, 10 to 100%) is preferable, more preferably 15% or more, and still more preferably 20% or more. When the solubility of the cationic curable polymer (A) is less than 10%, the alkali solubility of the resin composition may be insufficient.

  In the alkali-soluble resin composition of the present invention, the cationic polymerizable polymer (A) can be used alone or in combination of two or more.

  The content of the cationic curable polymer (A) in the alkali-soluble resin composition of the present invention (the total amount of these when two or more types are included) is not particularly limited, but the content of the alkali-soluble resin composition is not limited. 5% by weight or more (for example, 5 to 98% by weight) is preferable with respect to the total amount (100% by weight), more preferably 30% by weight or more (for example, 30 to 90% by weight), and further preferably 40% by weight or more. (For example, 40 to 80% by weight). When the content of the cationic curable polymer (A) is less than 5% by weight, the flexibility of the cured product obtained by curing the alkali-soluble resin composition may be insufficient.

[Alkali-soluble cationically polymerizable compound (B)]
The alkali-soluble cationically polymerizable compound (B) in the alkali-soluble resin composition of the present invention is a compound other than the cationically curable polymer (A), and is an alkali (alkaline aqueous solution; for example, 1% sodium hydrogen carbonate aqueous solution). ) -Soluble cationically polymerizable compound. The solubility (solubility at 23 ° C.) of the alkali-soluble cationically polymerizable compound (B) in a 1% sodium hydrogen carbonate aqueous solution is not particularly limited, but is 10% [g / 100 g-1% NaHCO ₃ aq] or more (for example, 10 to 10%). 100%), more preferably 15% or more, and still more preferably 20% or more. That is, as the alkali-soluble cationically polymerizable compound (B), for example, a compound having one or more cationically polymerizable groups in the molecule and having the solubility in a 1% aqueous sodium hydrogen carbonate solution of 10% or more. Can be mentioned.

  Examples of the cationic polymerizable group possessed by the alkali-soluble cationic polymerizable compound (B) include cationic polymerizable functional groups such as an epoxy ring (oxiranyl group), an oxetane ring (oxetanyl group), a vinyl ether group, and a vinyl aryl group. It is done.

  The number of cation polymerizable groups that the alkali-soluble cation polymerizable compound (B) has in the molecule may be one or more, and is not particularly limited, but is preferably 1 to 10, more preferably 1 to 5, More preferably, it is 1-3.

Specific examples of the alkali-soluble cationically polymerizable compound (B) include ethylene glycol diglycidyl ether, glycerol polyglycidyl ether, sorbitol polyglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl. Ether, diethylene glycol monovinyl ether, triethylene glycol monovinyl ether, tetraethylene glycol monovinyl ether, pentaethylene glycol monovinyl ether, oligoethylene glycol monovinyl ether, polyethylene glycol monovinyl ether, dipropylene glycol monovinyl ether, tripropylene glycol monovinyl ether, tetrapro Glycol monovinyl ether, pentaerythritol propylene glycol monomethyl ether, oligo propylene glycol monomethyl ether, polypropylene glycol monomethyl ether. Moreover, as an alkali-soluble cation polymeric compound (B), the compound represented by following formula (5) is also illustrated.

R ^a in the above formula (5) represents a monovalent hydrocarbon group. Examples of the monovalent hydrocarbon group include a monovalent aliphatic hydrocarbon group [for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, hexyl group, octyl group, isooctyl group, decyl group, Linear or branched C _1-20 alkyl group such as dodecyl group; vinyl group, allyl group, methallyl group, 1-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl Groups, 1-pentenyl groups, 2-pentenyl groups, 3-pentenyl groups, 4-pentenyl groups, 5-hexenyl groups and other C _2-20 alkenyl groups; ethynyl groups, propynyl groups and other C _2-20 alkynyl groups, etc. ], monovalent alicyclic hydrocarbon group [for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a C _3-12, such as cyclododecyl cycloalkyl Group; a cycloalkenyl group C _3-12, such as cyclohexenyl group; bicycloheptadiene group, such as cross-linked cyclic hydrocarbon group C _4-15, such as bicyclo heptenyl group, a monovalent aromatic hydrocarbon radical of [ For example, C _6-14 aryl group such as phenyl group, naphthyl group, anthryl group, etc.], monovalent group in which two or more of these groups are bonded [for example, cyclohexylmethyl group, methylcyclohexyl group, benzyl group, phenethyl Group, cinnamyl group, tolyl group, styryl group and the like]. Of these, a linear or branched alkyl group or a phenyl group is preferable. The monovalent hydrocarbon group may have various substituents such as a halogen atom, a hydroxyl group, and an alkoxy group.

R ^b in the above formula (5) represents a linear or branched alkylene group having 1 to 4 carbon atoms. Examples of the alkylene group include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, a trimethylene group, and a butylene group. Among these, an ethylene group [—CH ₂ CH ₂ —] and a propylene group [—CH ₂ CH (CH ₃ ) —] are preferable.

  M in the above formula (5) represents an integer of 1 or more. Although it does not specifically limit as m, The integer of 1-1000 is preferable, More preferably, it is an integer of 2-100, More preferably, it is an integer of 3-30.

  Examples of the compound represented by the above formula (5) include phenol penta (ethyleneoxy) glycidyl ether, lauryl alcohol pentadecyl (ethyleneoxy) glycidyl ether, and the like. The compound represented by the above formula (5) can be produced by a known or conventional method, and is not particularly limited. For example, an alkylene with respect to an alcohol such as an aliphatic higher alcohol, phenol, cresol, butylphenol or the like. It can be produced by adding polyether to obtain polyether alcohol, and further monoglycidyl etherification.

  Examples of the alkali-soluble cationically polymerizable compound (B) include commercial names such as “EX-810” (manufactured by Nagase ChemteX Corp.) and “EX-145” (manufactured by Nagase ChemteX Corp.). Can also be used.

  In the alkali-soluble resin composition of the present invention, the alkali-soluble cationically polymerizable compound (B) can be used alone or in combination of two or more.

  The content of the alkali-soluble cationic polymerizable compound (B) in the alkali-soluble resin composition of the present invention (the total amount of these when two or more are included) is not particularly limited, but the alkali-soluble resin composition 1 to 70% by weight is preferable with respect to (100% by weight), more preferably 5 to 60% by weight, and still more preferably 10 to 50% by weight. If the content is less than 1% by weight, the flexibility of the cured product may be insufficient. On the other hand, when the content exceeds 70% by weight, the heat resistance and curability of the cured product may be insufficient.

  Ratio of cationic curable polymer (A) and alkali-soluble cationic polymerizable compound (B) in the alkali-soluble resin composition of the present invention [cationic curable polymer (A) / alkali-soluble cationic polymerizable compound ( B)] (weight ratio) is not particularly limited, but is preferably 85/15 to 45/55, more preferably 80/20 to 50/50. If the ratio is out of the above range, it may be difficult to balance the flexibility, heat resistance, and transparency of the cured product.

[Cationic polymerization initiator (C)]
The alkali-soluble resin composition of the present invention further contains a cationic polymerization initiator (C) as an essential component. As the cationic polymerization initiator (C), a compound that initiates or accelerates cationic polymerization of the alkali-soluble resin composition can be used. Examples of the cationic polymerization initiator (C) include sulfonium salts such as triarylsulfonium hexafluorophosphate and triarylsulfonium hexafluoroantimonate; diaryliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, bis (dodecylphenyl) iodonium Examples include tetrakis (pentafluorophenyl) borate, iodonium salts such as iodonium [4- (4-methylphenyl-2-methylpropyl) phenyl] hexafluorophosphate; phosphonium salts such as tetrafluorophosphonium hexafluorophosphate; and pyridinium salts. .

  Examples of the cationic polymerization initiator (C) include proton acids such as perchloric acid, sulfuric acid, phosphoric acid, paratoluenesulfonic acid, trichloroacetic acid, trifluoroacetic acid; boron trifluoride, aluminum bromide, aluminum chloride. Lewis acids such as antimony pentachloride, ferric chloride, tin tetrachloride, titanium tetrachloride, mercury chloride, and zinc chloride can be used. In addition, iodine, triphenylchloromethane, and the like can also be used.

  In the alkali-soluble resin composition of the present invention, the cationic polymerization initiator (C) can be used alone or in combination of two or more. As the cationic polymerization initiator (C), for example, commercially available products such as a trade name “CPI-100P” (manufactured by San Apro Co., Ltd.) and a trade name “CPI-101A” (manufactured by San Apro Co., Ltd.) may be used. it can.

  The content of the cationic polymerization initiator (C) in the alkali-soluble resin composition of the present invention (the total amount of these when two or more are included) is not particularly limited, but is 100% by weight of the alkali-soluble resin composition. The content is preferably 0.01 to 50% by weight, more preferably 0.1 to 20% by weight.

  The alkali-soluble resin composition of the present invention has a cationically polymerizable compound other than the cationically curable polymer (A) and the alkali-soluble cationically polymerizable compound (B) (when referred to as “another cationically polymerizable compound”). May be included).

  Examples of the other cationic polymerizable compounds include cationic polymerizable compounds that are hardly soluble or insoluble in alkali (alkaline aqueous solution). As such a cationically polymerizable compound, for example, cationic polymerization having a solubility in 1% aqueous sodium hydrogen carbonate solution (solubility at 23 ° C.) of less than 10% (eg, 0% or more, less than 10%; preferably 5% or less). Compound.

  Examples of the other cationic polymerizable compounds include compounds having at least one cationic polymerizable group in the molecule such as an epoxy ring (oxiranyl group), an oxetane ring (oxetanyl group), a vinyl ether group, a vinyl aryl group, and an oxetanyl group. In addition, compounds that are hardly soluble or insoluble in an alkali (alkaline aqueous solution) can be mentioned. Specifically, as a compound having one or more epoxy rings in one molecule, for example, glycidyl methyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, Brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, epoxy novolac resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3,4-epoxycyclohexyl Methyl (3,4-epoxy) cyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane Tert-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ′, 4′-epoxy -6'-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol di (3,4-epoxycyclohexylmethyl) ether, ethylenebis (3,4-epoxycyclohexanecarboxy) Rate), dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol Glycidyl ether, trimethylolpropane triglycidyl ether, etc .; diglycidyl esters of aliphatic long-chain dibasic acids; monoglycidyl ethers of higher aliphatic alcohols; monoglycidyl ethers of phenol, cresol and butylphenol; glycidyl esters of higher fatty acids Etc.

  Examples of the compound having one or more oxetane rings in the molecule include trimethylene oxide, 3,3-bis (vinyloxymethyl) oxetane, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3- (2 -Ethylhexyloxymethyl) oxetane, 3-ethyl-3- (hydroxymethyl) oxetane, 3-ethyl-3-[(phenoxy) methyl] oxetane, 3-ethyl-3- (hexyloxymethyl) oxetane, 3-ethyl- 3- (chloromethyl) oxetane, 3,3-bis (chloromethyl) oxetane, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, bis {[1-ethyl (3-oxetanyl) ] Methyl} ether, 4,4′-bis [(3-ethyl-3-oxetanyl) methoxymethyl] Cyclohexyl, 1,4-bis [(3-ethyl-3-oxetanyl) methoxy] cyclohexane, 3-ethyl-3 {[(3-ethyloxetan-3-yl) methoxy] methyl} oxetane, and the like.

  Examples of the compound having one or more vinyl ether groups in the molecule include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxyisopropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxy Butyl vinyl ether, 2-hydroxybutyl vinyl ether, 3-hydroxyisobutyl vinyl ether, 2-hydroxyisobutyl vinyl ether, 1-methyl-3-hydroxypropyl vinyl ether, 1-methyl-2-hydroxypropyl vinyl ether, 1-hydroxymethylpropyl vinyl ether, 4- Hydroxycyclohexyl vinyl ether, 1,6-hexanediol monovinyl ether, 1,4-cyclohexanedi Tanol monovinyl ether, 1,3-cyclohexanedimethanol monovinyl ether, 1,2-cyclohexanedimethanol monovinyl ether, p-xylene glycol monovinyl ether, m-xylene glycol monovinyl ether, o-xylene glycol monovinyl ether, and derivatives thereof Etc.

  Examples of the compound having one or more vinylaryl groups in the molecule include styrene, divinylbenzene, methoxystyrene, ethoxystyrene, hydroxystyrene, vinylnaphthalene, vinylanthracene, 4-vinylphenyl acetate, (4-vinylphenyl) Examples thereof include dihydroxyborane, N- (4-vinylphenyl) maleimide, and derivatives thereof.

  In the alkali-soluble resin composition of the present invention, the other cationic polymerizable compounds may be used alone or in combination of two or more.

  The content of the other cationic polymerizable compound in the alkali-soluble resin composition of the present invention (the total amount of these other compounds when two or more are included) is not particularly limited, but the alkali-soluble resin composition (100 % By weight) is preferably 10% by weight or less (for example, 0 to 10% by weight), more preferably 5% by weight or less, and still more preferably 3% by weight or less. If the content exceeds 10% by weight, the alkali solubility of the resin composition may be insufficient.

  The alkali-soluble resin composition of the present invention may contain other additives as required within the range not impairing the effects of the present invention. Examples of the other additives include a curing swellable monomer, a photosensitizer (such as an anthracene sensitizer), a resin (excluding the cationic curable polymer (A)), an adhesion improver, a reinforcing agent, Examples of the additives include known or commonly used softeners, plasticizers, viscosity modifiers, solvents, inorganic or organic particles (such as nanoscale particles), organic-inorganic hybrid materials, and fluorosilanes.

  The alkali-soluble resin composition of the present invention only needs to contain at least the cationic curable polymer (A), the alkali-soluble cationic polymerizable compound (B), and the cationic polymerization initiator (C). The production method (preparation method) is not particularly limited. Specifically, for example, the alkali-soluble resin composition of the present invention can be prepared by stirring and mixing each component at a predetermined ratio and defoaming under vacuum as necessary. Further, for example, an alkali-soluble cationic polymerizable compound (B) (or an alkali-soluble cationic polymerizable compound (B) and other cationic polymerizable compounds) is used as a polymerization solvent, and the oxetane ring-containing ( By subjecting the monomer component containing the (meth) acryloyl compound (a1) and the radical polymerizable compound (a2) to radical polymerization, the cationic curable polymer (A) and the alkali-soluble cationic polymerizable compound (B) (or more A composition containing other cationic polymerizable compound) is obtained, and the alkali-soluble resin composition of the present invention can also be prepared by a method of blending the cationic polymerization initiator (C) therein.

<Hardened product>
A cured product can be obtained by curing (cationic curing) the alkali-soluble resin composition of the present invention. Cationic curing can be carried out by a known or conventional method, and is not particularly limited. However, a method of heating an alkali-soluble resin composition (particularly when a thermal cationic polymerization initiator is included), an alkali-soluble type, or the like. Examples include a method of irradiating the resin composition with active energy rays (light irradiation) (particularly when a photocationic polymerization initiator is included). In particular, it is preferable to advance curing by irradiation with active energy rays, and it is particularly preferable to advance curing by irradiation with active energy rays and heating from the viewpoint of easily obtaining a cured product with high shape accuracy.

  The active energy ray applied to the alkali-soluble resin composition is not particularly limited as long as it can initiate or advance a curing reaction (polymerization reaction). For example, X-rays, ultraviolet rays, visible rays, Infrared (near infrared, far infrared), electron beam, etc. are mentioned. Among these, ultraviolet rays are preferable because they are easy to handle. The active energy ray source is not particularly limited, and examples thereof include a mercury lamp, a xenon lamp, a carbon arc lamp, a metal halide lamp, sunlight, an electron beam source, and a laser light source.

The conditions for irradiating the active energy rays can be adjusted as appropriate under conditions that allow the alkali-soluble resin composition to be cured, and are not particularly limited. It is preferable to irradiate with an integrated light quantity of 3000 mJ / cm ² (more preferably 1500 to 2500 mJ / cm ² ). After irradiating the active energy ray, for example, heat treatment may be performed at a temperature of about 50 to 180 ° C. to further advance the curing reaction. In addition, the atmosphere at the time of irradiating the active energy ray is not particularly limited as long as it does not inhibit the curing reaction, and may be any of an air atmosphere, a nitrogen atmosphere, an argon atmosphere, and the like. The irradiation with active energy rays may be performed under normal pressure, or may be performed under reduced pressure or under pressure.

  A cured product having a desired shape can also be produced by curing and molding the alkali-soluble resin composition of the present invention by a known or conventional method. For example, a film-like cured product can be produced by applying (coating) an alkali-soluble resin composition on a flat substrate so as to have a desired thickness and then curing the composition. Further, a fiber-like cured product can also be produced by curing the alkali-soluble resin composition discharged from one end of a conduit such as a syringe in a thread form. In addition, a cured product having a desired shape can be produced by filling a mold (mold) with an alkali-soluble resin composition and then curing the resin composition. Moreover, the hardened | cured material of a desired shape can be manufactured also by cutting the hardened | cured material of an alkali-soluble type resin composition by a well-known thru | or usual means.

  As described above, the alkali-soluble resin composition of the present invention is soluble in alkali, and quickly cures when irradiated with active energy rays (particularly light), and has heat resistance and flexibility. In addition, an optical waveguide having a core and a clad (a lower clad and an upper clad) covering the core by a photolithography method using an alkaline aqueous solution as a developer can be formed. It can be preferably used for production. Hereinafter, a method for producing an optical waveguide using the alkali-soluble resin composition of the present invention will be described with reference to FIG.

  First, as shown to (1) of FIG. 2, the laminated body which has the lower layer clad 2 on the one surface of the base material 1 is used. The laminate can be obtained by a known or conventional method, and its production method is not particularly limited. For example, a curable composition (for example, the alkali-soluble resin composition of the present invention is formed on the surface of the substrate 1). ) Is applied (applied) and then cured (for example, cured by light irradiation), or a film-like lower clad 2 (for example, a film-like alkali-soluble material of the present invention). The cured product of the mold resin composition) and the substrate 1 can be obtained by a method of bonding them together.

  Next, as shown in (2) of FIG. 2, the alkali-soluble resin composition of the present invention is applied onto the lower clad 2 of the laminate to form a cation curable resin composition layer 3. . In addition, a known or conventional coating apparatus can be used for the coating, and is not particularly limited. For example, a known or conventional coating device such as a spin coater, a spray coater, a roll coater, an ink jet coater, or a comma coater is used. A construction device (coater) can be used.

  Next, as shown in (3) of FIG. 2, the cation curable resin composition layer 3 is irradiated with light through a photomask 4, and the cation curable resin in the exposed portion (the portion irradiated with the light). The composition layer 3 is cured. Thereafter, as shown in (4) of FIG. 2, the cation curable resin composition layer 3 in the unexposed portion (the portion not irradiated with light) is dissolved and removed with a developer which is an alkali (alkaline aqueous solution). (This operation may be referred to as “development”). In this way, the pattern of the core 6 can be formed on the lower clad 2 as shown in FIG. Since the alkali-soluble resin composition of the present invention is soluble in alkali, the cation-curable resin composition 3 in the unexposed area can be removed with high accuracy, and the core 6 can be formed with excellent shape accuracy. Can be formed. After the above development, it may be further washed (rinsed) with pure water or the like, if necessary.

  Thereafter, as shown in FIG. 2 (6), an optical waveguide can be obtained by covering the core 6 formed on the lower clad 2 with the upper clad 7. The upper clad 7 can be formed by a known or conventional method, and is not particularly limited. For example, the upper clad 7 is formed on the surface of the lower clad 2 and the core 5 (for example, the alkali-soluble resin composition of the present invention). ) Is applied (applied) and then cured (for example, cured by light irradiation). In addition, the coating of the curable composition can be performed using the above-described known or conventional coating apparatus (for example, the above-described coating apparatus).

  The optical waveguide I produced in this manner is an optical waveguide containing a cured product of the alkali-soluble resin composition of the present invention [one or both of the core and the clad (upper clad, lower clad) are those of the present invention. Since the optical waveguide is formed of a cured product of an alkali-soluble resin composition], it has a low light loss and is excellent in heat resistance and flexibility.

  Since the alkali-soluble resin composition of the present invention can form a cured product having excellent transparency, heat resistance, and flexibility, it can be preferably used for applications requiring these characteristics. Specifically, the alkali-soluble resin composition of the present invention is not limited to the above-mentioned optical waveguide (use as a resin composition for optical waveguide material), but also includes, for example, optical fibers, stress relaxation adhesives, sealing It can be preferably used in various applications such as an agent, underfill, ink-jet ink, color filter, nanoimprint, and flexible substrate.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, the compounding quantity of each component of the cation curable resin composition (alkali-soluble resin composition) in Table 1 and Table 2 was shown by the weight part. Moreover, the compounding quantity of the cationic curable polymer (liquid resin) was shown in terms of the amount of monomer constituting the polymer (monomer composition).

Production Example 1
(Production of cationic curable polymer)
A 5-neck flask equipped with a monomer dropping line, an initiator dropping line, a thermometer, a reflux tube, and a stirring blade is charged with 367 g of 1-methoxy-2-acetoxypropane (PGMEA) and heated to 85 ± 1 ° C. under a nitrogen stream. did. Next, while stirring this, 630 g of PGMEA, 240 g (0.94 mol) of 3-ethyl-3- (3-acryloyloxy-2,2-dimethylpropyloxymethyl) oxetane (EOXTM-NPAL), n-butyl acrylate (BA) ) 600 g (4.68 mol), 210 g (2.43 mol) of methacrylic acid (MAA), and 2,2′-azobis (isobutyric acid) dimethyl (trade name “V-601”, manufactured by Wako Pure Chemical Industries, Ltd.) 0.74 g of the mixed liquid was dropped over 5 hours with a liquid feed pump. After completion of dropping, the mixture was further maintained for 2 hours, and then cooled to 40 ° C. or lower to obtain a resin composition. This was diluted with 2100 g of PGMEA, purified by reprecipitation with 5 times amount (weight conversion) of 60 wt% methanol aqueous solution, and kept in a vacuum dryer (40 ° C., full vacuum) for 60 hours to obtain a colorless transparent liquid. Resin (1) (cationic curable polymer) was obtained.
The liquid resin (1) had a polystyrene equivalent weight average molecular weight of 219,000 and a number average molecular weight of 45,500.

Production Example 2
(Production of cationic curable polymer)
A 5-neck flask equipped with a monomer dropping line, an initiator dropping line, a thermometer, a reflux tube, and a stirring blade was charged with 391 g of PGMEA and heated to 85 ± 1 ° C. under a nitrogen stream. Next, while stirring this, 670 g of PGMEA, 72 g (0.28 mol) of EOXTM-NPAL, 108 g (0.84 mol) of BA, 117 g (1.13 mol) of styrene (St), 74 g (0.86 mol) of MAA, and “V-601” 57.4 g of the mixed solution was dropped over 5 hours with a liquid feed pump. After completion of dropping, the mixture was further maintained for 2 hours, and then cooled to 40 ° C. or lower to obtain a resin composition. This was purified by reprecipitation with a 5-fold (by weight) 60% by weight aqueous methanol solution, and kept in a vacuum dryer (40 ° C., full vacuum) for 60 hours, whereby a colorless transparent liquid resin (2) (cation) A curable polymer) was obtained.
The liquid resin (2) had a polystyrene equivalent weight average molecular weight of 4,000 and a number average molecular weight of 2,400.

Production Example 3
The amount of EOXTM-NPAL used is 270 g (1.05 mol), the amount of BA used is 675 g (4.10 mol), the amount of MAA used is 104 g (1.21 mol), and the amount of “V-601” used is 0.69 g. A liquid resin (3) (cation curable polymer) was obtained in the same manner as in Production Example 1 except that
The liquid resin (3) had a polystyrene equivalent weight average molecular weight of 225,000 and a number average molecular weight of 47,200.

Production Example 4
The amount of EOXTM-NPAL used is 210 g (0.82 mol), the amount of BA used is 525 g (4.10 mol), the amount of MAA used is 315 g (3.66 mol), and the amount of “V-601” used is 0.79 g. A liquid resin (4) (cationic curable polymer) was obtained in the same manner as in Production Example 1 except that
The liquid resin (4) had a polystyrene equivalent weight average molecular weight of 209,000 and a number average molecular weight of 44,300.

Production Example 5
The amount of EOXTM-NPAL used is 82 g (0.32 mol), the amount of BA used is 123 g (0.96 mol), the amount of St used is 133 g (1.28 mol), the amount of MAA used is 36 g (0.42 mol), Except having changed the usage-amount of "V-601" into 54.9g, it carried out similarly to manufacture example 2, and obtained liquid resin (5) (cationic curable polymer).
The liquid resin (5) had a polystyrene equivalent weight average molecular weight of 4,300 and a number average molecular weight of 2,500.

Production Example 6
The amount of EOXTM-NPAL used is 63 g (0.25 mol), the amount of BA used is 95 g (0.74 mol), the amount of St used is 102 g (0.98 mol), the amount of MAA used is 112 g (1.30 mol), Except having changed the usage-amount of "V-601" into 60.2g, it carried out similarly to manufacture example 2, and obtained liquid resin (6) (cationic curable polymer).
The liquid resin (6) had a polystyrene-equivalent weight average molecular weight of 3,700 and a number average molecular weight of 2,200.

Production Example 7
EOXTM-NPAL usage was changed to 300 g (1.17 mol), BA usage was changed to 750 g (5.85 mol), “V-601” usage was changed to 0.65 g, and MAA was not used Produced liquid resin (7) (cationic curable polymer) in the same manner as in Production Example 1.
The liquid resin (7) had a polystyrene equivalent weight average molecular weight of 235,700 and a number average molecular weight of 50,000.

Production Example 8
The amount of EOXTM-NPAL used is 280 g (1.09 mol), the amount of BA used is 700 g (5.46 mol), the amount of MAA used is 56 g (0.66 mol), and the amount of “V-601” used is 0.66 g. A liquid resin (8) (cationic curable polymer) was obtained in the same manner as in Production Example 1 except that
The liquid resin (8) had a polystyrene equivalent weight average molecular weight of 230,100 and a number average molecular weight of 48,700.

Production Example 9
The amount of EOXTM-NPAL used is 150 g (0.59 mol), the amount of BA used is 375 g (2.93 mol), the amount of MAA used is 524 g (6.09 mol), and the amount of “V-601” used is 0.88 g. A liquid resin (9) (cationic curable polymer) was obtained in the same manner as in Production Example 1 except that
The liquid resin (9) had a polystyrene equivalent weight average molecular weight of 199,000 and a number average molecular weight of 43,200.

Production Example 10
The usage amount of EOXTM-NPAL is 90 g (0.35 mol), the usage amount of BA is 136 g (2.93 mol), the usage amount of St is 147 g (1.40 mol), the usage amount of “V-601” is 51.8 g. A liquid resin (10) (cationic curable polymer) was obtained in the same manner as in Production Example 2 except that MAA was not used.
The liquid resin (10) had a weight average molecular weight in terms of polystyrene of 4,500 and a number average molecular weight of 2,700.

Production Example 11
The amount of EOXTM-NPAL used is 86 g (0.34 mol), the amount of BA used is 129 g (1.01 mol), the amount of St used is 140 g (1.34 mol), the amount of MAA used is 17 g (0.20 mol), Except having changed the usage-amount of "V-601" into 53.2 g, it carried out similarly to manufacture example 2, and obtained liquid resin (11) (cationic curable polymer).
The liquid resin (11) had a polystyrene equivalent weight average molecular weight of 4,400 and a number average molecular weight of 2,600.

Production Example 12
The amount of EOXTM-NPAL used is 45 g (0.18 mol), the amount of BA used is 68 g (0.53 mol), the amount of St used is 73 g (0.70 mol), the amount of MAA used is 189 g (2.19 mol), Except having changed the usage-amount of "V-601" to 66.29g, it carried out similarly to manufacture example 2, and obtained liquid resin (12) (cationic curable polymer).
The liquid resin (12) had a polystyrene-equivalent weight average molecular weight of 3,500 and a number average molecular weight of 2,000.

Examples 1-12, Comparative Examples 1-6
(Production of cationic curable resin composition)
According to the composition and amount shown in Tables 1 and 2, the cationic curable polymers (liquid resins (1) to (12)), alkali-soluble cationic polymerizable compounds, and cationic polymerization initiators obtained in Production Examples 1 to 12 were used. A cation curable resin composition (alkali-soluble resin composition) was prepared by mixing and dissolving and filtering with a filter having a pore size of 0.2 μm.
Further, the above cationic curable resin composition was applied on a non-silicone release film substrate (trade name “T789”, manufactured by Daicel Value Coating Co., Ltd.) with an applicator so as to have a thickness of about 100 μm. A film-like cured product (thickness) by irradiating with ultraviolet rays (irradiation energy: about 2J, wavelength: 320-390 nm) using an ultraviolet irradiation device (trade name “UVC-02516S1AA02”, manufactured by USHIO INC.) : About 100 μm).

In addition, the symbol in Table 1 and Table 2 shows the following compound.
EOXTM-NPAL: 3-ethyl-3- (3-acryloyloxy-2,2-dimethylpropyloxymethyl) oxetane BA: n-butyl acrylate St: styrene MAA: methacrylic acid EX-810: ethylene glycol diglycidyl ether (Nagase) Product name "EX-810" manufactured by Chemtex Co., Ltd.)
EX-145: Phenolpenta (ethyleneoxy) glycidyl ether (manufactured by Nagase ChemteX Corporation, trade name “EX-145”)
CPI-100P: a mixture of diphenyl [4- (phenylthio) phenyl] sulfonium hexafluorophosphate, thiodi-p-phenylenebis (diphenylsulfonium), bis (hexafluorophosphate), propylene carbonate, and diphenyl sulfide (San Apro Corp. ) Product name "CPI-100P")

(Evaluation of alkali solubility)
The cationic curable resin compositions obtained in Examples 1 to 12 and Comparative Examples 1 to 6 were uniformly applied on a silicon wafer using a spin coater, irradiated with ultraviolet rays through a photomask, Cured. Subsequently, it was immersed for 1 minute in 20 mL of 1% sodium hydrogencarbonate aqueous solution at normal temperature (23 degreeC), and also wash | cleaned with 50 mL ion-exchange water. Thereafter, it is visually confirmed whether or not the resin (cationic curable resin composition) remains in the non-exposed portion. When it does not remain, ○ (alkali solubility is good), and when it remains, × (alkali solubility). Bad). The results are shown in Tables 1 and 2.

(Evaluation of heat resistance)
The cured products obtained in Examples 1 to 12 and Comparative Examples 1 to 6 were subjected to thermogravimetric analysis [measurement temperature: 30 to 550 ° C., temperature increase temperature: 5 ° C./min, under nitrogen atmosphere], and the thermal decomposition temperature was measured. did. As shown in FIG. 1, the tangent line where there is no initial weight loss or gradually decreasing (straight line extending from the portion where there is almost no weight reduction) and the inflection point where the weight loss suddenly occurs The temperature at the point where the tangent line intersects was defined as the thermal decomposition temperature (T). And the heat resistance of hardened | cured material was evaluated on the following reference | standard.
Evaluation criteria: A case where the thermal decomposition temperature (T) was 260 ° C. or higher was evaluated as “Good” (good heat resistance), and a case where the thermal decomposition temperature (T) was lower than 260 ° C. was evaluated as “No” (heat resistance poor). The results are shown in Tables 1 and 2.

(Evaluation of flexibility)
The cured products (film shape, thickness 100 μm) obtained in Examples 1 to 12 and Comparative Examples 1 to 6 were wrapped around a rod with a radius of 2 mm, and the presence or absence of cracks (cracks) was visually observed. evaluated.
Evaluation criteria: A case where no crack (crack) was found in the film-like cured product was evaluated as ○ (good flexibility), and a case where a crack (crack) was found in the film-like cured product was evaluated as x (poor flexibility). . The results are shown in Tables 1 and 2.

(Evaluation of transparency)
The total light transmittance and haze of the cured products (film shape, thickness 100 μm) obtained in Examples 1 to 12 and Comparative Examples 1 to 6 were measured for color separation and turbidity measuring instrument (manufactured by Nippon Denshoku Kogyo Co., Ltd.). , “300A”). Transparency was evaluated according to the following criteria.
Evaluation criteria: A case where the total light transmittance was 90% or more and the haze was 10% or less (good transparency), the total light transmittance was less than 90% and / or the haze exceeded 10%. The case was evaluated as x (poor transparency). The results are shown in Tables 1 and 2.

Example 13
(Manufacture of polymer optical waveguide)
A polymer optical waveguide was manufactured according to the procedure shown in FIG.
[Formation of lower cladding]
On the silicon wafer (base material), the cationic curable resin composition obtained in Example 2 was uniformly applied using a spin coater (Mikasa Spin Coater IH-DX), and then the entire surface of the applied coating film was irradiated with ultraviolet rays. Irradiate ultraviolet rays using an irradiation device (Mikasa mask aligner MA60-F) (irradiation energy: about 2 J, wavelength: 320 to 390 nm), and then heat at 90 ° C. for 5 minutes in a dryer to cure the coating film. A lower cladding was formed (see (1) in FIG. 2). The thickness of the lower clad was about 30 μm.
[Formation of core]
Using an RIE apparatus (manufactured by Nidec Anelva Co., Ltd.), the surface of the lower clad was subjected to oxygen RIE treatment, and then the cationic curable resin composition obtained in Example 9 was applied to the lower clad using a spin coater. (See (2) in FIG. 2), and a photomask was pressed and selectively irradiated (exposed) with ultraviolet rays (irradiation energy: about 2 J, wavelength 320 to 390 nm) ((3) in FIG. 2) And (4)). After the exposure, heating was performed at 90 ° C. for 5 minutes in a dryer, followed by washing with a 1% aqueous sodium hydrogen carbonate solution and ion-exchanged water at room temperature (23 ° C.). Furthermore, it heated at 90 degreeC for 5 minute (s) in dryer, and formed one core as shown to (5) of FIG. The thickness of the formed core was about 40 μm.
[Formation of upper cladding]
After the surface on which the core is formed is subjected to oxygen RIE treatment, the cationic curable resin composition obtained in Example 2 is uniformly applied using a spin coater, and then the entire surface of the applied coating film is irradiated with ultraviolet rays. (Irradiation energy: about 2 J, wavelength: 320 to 390 nm), heated in a dryer at 90 ° C. for 5 minutes to cure the coating film, formed an upper clad, and obtained an optical waveguide (polymer optical waveguide) (See (6) in FIG. 2). The total film thickness of the polymer optical waveguide including the formed upper cladding was about 100 μm.

(Evaluation of flexibility)
When the polymer optical waveguide obtained in Example 13 was wound around a rod having a radius of 1 mm, the presence or absence of the occurrence of cracks (cracks) was visually confirmed, and the case where no cracks (cracks) occurred was acceptable (flexible) It was determined that the property was good.
As a result, no cracks (cracks) were observed and the test was successful.

(Evaluation of heat resistance)
The polymer optical waveguide obtained in Example 13 was heated at 260 ° C. for 30 seconds, and the case where the difference in optical loss before and after heating was 0.1 dB / cm or less was determined to be acceptable (good heat resistance). The optical loss before and after heating was measured by the same method as described in “Evaluation of optical loss” below.
As a result, the difference in light loss before and after heating was 0.1 dB / cm or less, which was acceptable.

(Evaluation of optical loss)
Light emitted from a light source (ADVANTEST Q81201) having a wavelength of 857 nm is introduced into the polymer optical waveguide obtained in Example 13 through a matching oil through a matching oil using a GI fiber having a core diameter of 50 μm. Was received by a PCF fiber having a core diameter of 200 μm through matching oil, and connected to a power meter (ADVANTEST Q82220, OPTICAL SENSOR Q82214) to measure the emitted light with a power meter. The optical loss of the linear portion of the polymer optical waveguide determined by the cutback method was 0.1 dB / cm.

DESCRIPTION OF SYMBOLS 1 Base material 2 Lower layer clad 3 Cationic curable resin composition layer 4 Photomask 5 Light source 6 Core 7 Upper layer clad I Optical waveguide (polymer optical waveguide)

Claims (6)

Following formula (1)

[In Formula (1), R < ¹ >, R < ² > is the same or different and shows a hydrogen atom or an alkyl group. A represents a linear or branched alkylene group having 2 to 20 carbon atoms. ]
A cationically curable polymer that is a radical copolymer of a monomer component containing an oxetane ring-containing (meth) acryloyl compound (a1) and a radically polymerizable compound (a2) having an alkali-soluble group in the molecule ( A), an alkali-soluble cationic polymerizable compound (B) other than the cationic curable polymer (A), and a cationic polymerization initiator (C), wherein the acid value is 40 to 200 mgKOH / g An alkali-soluble resin composition. The cationic curable polymer (A) is an oxetane ring-containing (meth) acryloyl compound (a1), a radical polymerizable compound (a2) having an alkali-soluble group in the molecule, and a radical other than (a1) and (a2). A radical copolymer of a monomer component containing a polymerizable compound (a3),
The radical polymerizable compound (a3) is selected from the group consisting of (meth) acryloyl group, (meth) acryloyloxy group, (meth) acryloylamino group, vinylaryl group, vinyl ether group, and vinyloxycarbonyl group. The alkali-soluble resin composition according to claim 1, which is a compound having only one group in the molecule.   The ratio of the cation curable polymer (A) to the alkali-soluble cation polymerizable compound (B) [cation curable polymer (A) / alkali-soluble cation polymerizable compound (B)] (weight ratio) is 85/15 to The alkali-soluble resin composition according to claim 1 or 2, which is 45/55.   It is a resin composition for optical waveguide materials, The alkali-soluble resin composition of any one of Claims 1-3.   Hardened | cured material obtained by hardening the alkali-soluble type resin composition of any one of Claims 1-4 by active energy ray irradiation and a heating.   An optical waveguide comprising the cured product according to claim 5.

Images