JP2012126888A - Adhesive including cyclic acetal compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive that is decomposed by an acid and can be released.SOLUTION: The adhesive is composed of a cyclic acetal compound represented by formula (1) (wherein Rrepresents a residue of a carbonyl compound; R, R, Rto Rare the same or different, and each represents a hydrogen atom or a substituent; Rrepresents a substituent; and Ror Rand Rmay bond to each other to form a ring).

Description

  The present invention relates to a novel adhesive containing a compound having a cyclic structure (cyclic acetal structure) (cyclic acetal compound), and an adhesion method (temporary adhesion method) using this adhesive.

  The semiconductor manufacturing process includes a process of polishing (or grinding) the back surface of a wafer on which a pattern is formed (back grinding process) and a process of cutting a wafer thinned by polishing into chips (dicing process). In the back grinding process, in order to protect the wafer during polishing, the back grind tape is usually peeled off after the back side of the wafer bonded and laminated with a back grind tape as a protective sheet is thinned in advance. A wafer has been obtained. Specifically, the back grind tape is composed of at least an adhesive layer (adhesive layer), and this adhesive layer is adhered to the wafer.

  Therefore, the adhesive layer of the back grind tape is required to have sufficient adhesion enough to protect (fix) the wafer even by polishing and easy peeling after polishing. At present, it is generally formed of a curable resin because it utilizes adhesiveness (adhesiveness) and releasability due to curing shrinkage. For example, Japanese Patent Laid-Open No. 2001-200215 (Patent Document 1) discloses a pressure-sensitive adhesive sheet that is used when processing a semiconductor wafer and is attached to the surface of the semiconductor wafer to hold and protect the semiconductor wafer. There is disclosed a pressure-sensitive adhesive sheet for processing a semiconductor wafer, wherein a radiation non-curable pressure-sensitive adhesive layer is formed on the surface, and a radiation-curable pressure-sensitive adhesive layer that is cured by radiation and has reduced adhesive strength is provided on the surface thereof. Yes.

  However, in the method using such a curable resin, sufficient peelability cannot be ensured, and the adhesive layer remains on the wafer, or such a residual adhesive layer cannot be sufficiently separated from the wafer. There is a case. In addition, after the adhesive layer is cured, a process of peeling the wafer and the protective sheet (adhesive layer) is required. However, when the film is peeled off, the already thinned wafer may be cracked.

JP 2001-200215 A (Claims)

  Accordingly, an object of the present invention is to provide a novel adhesive comprising a cyclic acetal compound having a cyclic structure (cyclic acetal structure) as an adhesive component, and a bonding method (temporary bonding or temporary fixing method) using the adhesive. It is in.

  Another object of the present invention is to use an adhesive capable of being decomposed by the action of an acid and exhibiting excellent peelability despite having adhesiveness (for example, thermal adhesiveness) and the adhesive. It is to provide a bonding method (temporary bonding or temporary fixing method).

  Still another object of the present invention is a material to be polished (for example, a wafer such as a semiconductor wafer) that can improve or improve the separation property (peelability) from the polishing agent (wafer or the like) after polishing (after back grinding). Is to provide a processing method (manufacturing method of a polished material to be polished (wafer or the like)).

  As adhesives or pressure-sensitive adhesives that can exhibit releasability like the pressure-sensitive adhesive layer of the back-grind tape (or back-grind film or back-grind sheet), those that utilize curing shrinkage have been the mainstream. Under such circumstances, carbonyl compounds have been studied as a result of diligent research to achieve the above-mentioned problems, based on a completely different idea of searching for a material that exhibits the peelability by decomposing the adhesive material itself. A compound having a specific cyclic acetal structure obtained by a reaction of a vinyl ether compound (for example, a polycarbonyl compound such as a dialdehyde compound) has adhesiveness or adhesiveness (for example, hot melt adhesiveness or thermal adhesiveness). And it can be suitably used as an adhesive, and such a compound or adhesive can easily exhibit releasability because it decomposes (lower molecular weight) by the action of an acid (that is, lowers the adhesiveness). Useful as an adhesive (adhesive for temporary fixing) for temporarily fixing (fixing temporarily fixed) an adherend (for example, back grinding) Found to be useful) as an adhesive constituting the sheet used for the protection of the object to be polished (such as a wafer) in the process, thereby completing the present invention.

  That is, the adhesive of the present invention has the following formula (1)

Wherein R ¹ is a residue of a carbonyl compound, R ^2a and R ^2b are the same or different and are a hydrogen atom or a substituent, R ^{3 to} R ⁵ are the same or different and are a hydrogen atom or a substituent, and R ⁶ is a substituent. R ³ or R ⁴ and R ⁶ may be bonded to each other to form a ring.)
The cyclic acetal compound which has a unit represented by these is included.

In formula (1), R ¹ may in particular be a residue of a polycarbonyl compound. Such a cyclic acetal compound in which R ¹ is a residue of a polycarbonyl compound may be a multimeric compound having a unit represented by the formula (1) as a repeating unit.

In the formula (1), R ¹ may be a direct bond or a divalent hydrocarbon group. In the formula (1), R ^2a and R ^2b may be hydrogen atoms, and R ^{3 to} R ⁵ may be hydrogen atoms or hydrocarbon groups.

In the formula (1), the cyclic acetal compound is a unit (1a) in which R ⁶ is a non-polymerizable substituent (for example, a non-polymerizable hydrocarbon group such as a saturated aliphatic hydrocarbon group) (that is, the following formula ( A unit represented by 1a), and R ⁶ is a polymerizable substituent (for example, an unsaturated aliphatic hydrocarbon group or a hydrocarbon group having a polymerizable group such as a hydrocarbon group having a polymerizable group). It may have at least one unit selected from (1b) (that is, a unit represented by the following formula (1b)) (for example, it may have as a repeating unit).

(In the formula, R ^6a represents a non-polymerizable substituent, R ^6b represents a polymerizable substituent, and R ¹ , R ^2a , R ^2b , R ³ , R ⁴ and R ⁵ are the same as described above.)
A typical cyclic acetal compound is represented by the formula (1), wherein R ¹ is a direct bond, a divalent saturated aliphatic hydrocarbon group (for example, an alkylene group) or a divalent aromatic hydrocarbon group (for example, an arylene group). R ^2a and R ^2b are hydrogen atoms, R ^{3 to} R ⁵ are the same or different and are a hydrogen atom or a saturated aliphatic hydrocarbon group (for example, an alkyl group such as a methyl group), and the unit ( In 1a), the non-polymerizable substituent is a saturated aliphatic hydrocarbon group (for example, an alkyl group, an alkoxyalkyl group, an alkoxy (poly) alkoxyalkyl group or a cycloalkyl group), and in the unit (1b), a polymerizable substituent A hydrocarbon group having an unsaturated aliphatic hydrocarbon group (for example, alkenyl group) or a polymerizable group [for example, having a (meth) acryloyloxy group Reduction (such as an alkyl group) hydrogen radical in which includes compounds.

In the formula (1), R ¹ may be an asymmetric arylene group such as a 1,2-phenylene group or a 1,3-phenylene group.

The cyclic acetal compound has at least a unit (1a) in which R ⁶ is a non-polymerizable substituent, and the non-polymerizable substituent is a secondary or tertiary saturated aliphatic hydrocarbon group (for example, Secondary or tertiary alkyl group, cycloalkyl group, etc.).

Further, the cyclic acetal compound, which may be the least have a unit in which R ⁶ is a polymerizable substituent (1b), in particular, the unit R ⁶ is a non-polymerizable substituent (1a), R ⁶ May have a unit (1b) which is a polymerizable substituent. In the multimeric compound having such unit (1a) and unit (1b), the ratio (molar ratio) of unit (1a) to unit (1b) is, for example, the former / the latter = 99/1 to 40/60. It may be a degree.

  The cyclic acetal compound may have a weight average molecular weight of, for example, 800 or more. Further, the cyclic acetal compound (or multimeric compound) is excellent in heat resistance, for example, a 5 wt% reduction temperature (a temperature at which 5 wt% is reduced or decomposed in simultaneous differential heat and thermogravimetric measurement) is 150 ° C. or more. It may be a compound of The cyclic acetal compound is usually solid at normal temperature and may have hot melt adhesiveness.

  The adhesive of the present invention may further contain an acid generator. Such an adhesive may in particular be a temporary fixing adhesive (for example, an adhesive for fixing the wafer during polishing).

  In the present invention, an adhering step of adhering an adherend using the adhesive (adhesive containing an acid generator), and among the adhered adherend, at least an active energy ray (active light beam, active light ray) A decomposition step of decomposing the adhesive with the acid generated from the acid generator by irradiation (or application) of heat rays, etc., and a separation step of separating the adherend and the decomposed adhesive from the adhered adherend A method for temporarily bonding an adherend including

  Further, the present invention comprises an adhesion process for obtaining a laminate by adhering the adhesive (adhesive containing an acid generator) and an object to be polished (wafer or the like) as an adherend, and the laminate. Of the material to be polished (such as a wafer), a polishing process for polishing the surface opposite to the bonding surface, and at least the bonding interface of the polished laminate is irradiated (or imparted) with active energy rays to generate acid. A wafer comprising: a decomposition step of decomposing the adhesive with an acid generated from the agent; and a separation step of separating the polished material (wafer or the like) as an adherend from the laminate and the decomposed adhesive Processing methods are also included.

  In the bonding step of these methods, an adhesive that is solid at room temperature may be used and bonded by hot melt. Typically, in the bonding step, the adhesive and the adherend may be brought into contact with each other at 50 to 150 ° C. for bonding. In the separation step, the adherend may be slid with respect to the adhesive (the adherend is slid relative to the adhesive) to be separated. The method may further include a cleaning step of cleaning an adhesive surface of the adherend with the adhesive after the separation step.

  The adhesive of the present invention contains a cyclic acetal compound having a cyclic structure (cyclic acetal structure). Such an adhesive of the present invention can exhibit excellent peelability by being decomposed by the action of an acid, despite having adhesiveness (for example, thermal adhesiveness). Therefore, it is suitable as an adhesive (adhesive for temporary fixing) or the like that requires both adhesiveness and peelability such as an adhesive layer of a back grind tape. Further, in the processing method of a material to be polished (wafer or the like) of the present invention, since the release property is expressed by decomposing the adhesive itself, the material from the material to be polished (wafer or the like) after polishing (after back grinding treatment) is developed. Separability (peelability) can be improved or improved.

  The adhesive of the present invention contains at least a compound having a specific cyclic acetal structure. That is, such a cyclic acetal compound has adhesiveness and constitutes an adhesive component of the adhesive of the present invention.

[Cyclic acetal compound]
(Unit represented by Formula (1))
The cyclic acetal compound has the following formula (1)

Wherein R ¹ is a residue of a carbonyl compound, R ^2a and R ^2b are the same or different and are a hydrogen atom or a substituent, R ^{3 to} R ⁵ are the same or different and are a hydrogen atom or a substituent, and R ⁶ is a substituent. R ³ or R ⁴ and R ⁶ may be bonded to each other to form a ring.)
It is a compound which has a unit represented by these.

  Such a cyclic acetal compound has a cyclic acetal skeleton as described above. As will be described later, usually a carbonyl compound [particularly, a polycarbonyl compound (a compound having at least two carbonyl groups)] and a vinyl ether. It is a cyclic acetal compound obtained by reacting with a system compound.

The group R ^{1 in} the above formula (1) is a residue of a carbonyl compound (or acyl compound). Such a residue can be selected according to the number of acyl groups of the carbonyl compound, and is a monovalent group when the carbonyl compound is a monocarbonyl compound (or a monoacyl compound or a compound having one acyl group). On the other hand, when the carbonyl compound is a polycarbonyl compound (or a polyacyl compound or a compound having two or more acyl groups), it becomes a monovalent group or a polyvalent group (for example, a divalent group).

  That is, as will be described later, the cyclic acetal structure is formed by the reaction of one acyl group of a carbonyl compound, one acyl group of another carbonyl compound, and a vinyl ether compound, so that the carbonyl compound is a polycarbonyl compound. In this case, the cyclic acetal compound is usually a compound having a unit represented by the formula (1) as a repeating unit (multimeric compound).

When the carbonyl compound is a monocarbonyl compound (or a monoacyl compound or a compound having one acyl group) (or when R ¹ is a monovalent group), the cyclic acetal compound is represented by the following formula (1A). Is done.

(In the formula, R ¹ , R ^2a , R ³ , R ⁴ , R ⁵ , and R ⁶ are the same as described above.)
The cyclic acetal compound may be a compound represented by the above formula (1A) as long as it has adhesiveness (for example, as long as it is solid), but it efficiently balances adhesiveness and acid decomposability. From the viewpoint, a compound (multimeric compound) having a unit represented by the formula (1) as a repeating unit is preferable.

In such formula (1) (or formula (1A)), R ¹ can be selected according to the type of the carbonyl compound as described above, for example, a residue of a polycarbonyl compound [particularly, a polycarbonyl compound. ) Group obtained by removing two acyl groups (for example, formyl group) (divalent group)], for example, direct bond (-), aliphatic hydrocarbon group [or divalent aliphatic hydrocarbon group, for example, alkylene A group (for example, a C _1-12 alkylene group such as a methylene group, an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, preferably a C _2-10 alkylene group, more preferably a C _{2 -6} etc. alkylene group), a cycloalkylene group (e.g., a C _5-8 cycloalkylene group such as cyclohexylene) saturated aliphatic such as hydrocarbons Element group], aromatic hydrocarbon group [or divalent aromatic hydrocarbon group, for example, arylene group (for example, phenylene group (o, m or p-phenylene group), methylphenylene group, dimethylphenylene group, naphthylene group) A C _6-14 arylene group, preferably a C _6-12 arylene group, more preferably a C _6-10 arylene group, etc.] and the like; A valent group (in the case of formula (1A)), for example, hydrogen atom, hydrocarbon group {for example, aliphatic hydrocarbon group [for example, C _1-12 such as alkyl group (for example, methyl group, ethyl group, propyl group, etc. alkyl group, preferably a _{C 2-10} alkyl group, more preferably such _{C 2-6} alkyl groups), _{C 5-8} Shikuroa such cycloalkyl group (e.g., cyclohexyl group Kill group) saturated monovalent aliphatic hydrocarbon group, such as, an aromatic hydrocarbon group [or a monovalent aromatic hydrocarbon group, for example, an aryl group (e.g., phenyl group, a naphthyl group C _{6- 14} aryl group, preferably C _6-12 aryl group, more preferably C _6-10 aryl group, etc.] and the like}.

Such a hydrocarbon group may have a substituent. Examples of the substituent include an oxygen atom-containing group {for example, a hydroxyl group, an alkoxy group (for example, a C _1-10 alkoxy group such as a methoxy group, an ethoxy group, and a propoxy group, preferably a C _1-6 alkoxy group, more preferably Is a C _1-4 alkoxy group; an aralkyloxy group such as a benzyloxy group or a phenethyloxy group (for example, a C _6-10 aryl C _1-4 alkoxy group), a carboxyl group, an acyl group [for example, an alkanoyl group (for example, A C _1-10 alkanoyl group such as a formyl group, an acetyl group or an n-propanoyl group, preferably a C _2-6 alkanoyl group), an aroyl group (eg, a C _7-11 aroyl group such as a benzoyl group, etc.)] , an alkoxycarbonyl group (e.g., _{C 1-4} alkoxy such as methoxy carbonyl group Carbonyl group, etc.}, nitrogen atom-containing groups [eg, nitro group, cyano group, amino group, substituted amino group (eg, mono- or dialkylamino group such as N, N-dimethylamino group, etc.)], halogen atom (Fluorine atom, chlorine atom, bromine atom, iodine atom, etc.).

The group R ¹ (hydrocarbon group) may have a substituent alone or in combination of two or more. When the hydrocarbon group has a substituent, the number of substituents may be, for example, 1 to 8, preferably 1 to 5, and more preferably about 1 to 3.

In the multimeric compound, the cyclic acetal structure is usually formed by an acyl group of a polycarbonyl compound and a vinyl group portion of a vinyl ether compound, as will be described later. Therefore, when the group R ¹ has an acyl group (for example, a formyl group) as a substituent (that is, when the polycarbonyl compound has an acyl group of 3 or more (for example, about 3 to 6, preferably about 3 to 4)). The multimeric compound may have an acyl group as a substituent only, and may be a compound in which a unit represented by the formula (1) is further bonded via an acyl group as the substituent. In such a case, the multimeric compound may form a branched chain or branched network structure.

Representative groups R ¹ include hydrocarbon groups (divalent hydrocarbon groups) such as alkylene groups (eg, C _2-5 alkylene groups) and arylene groups (eg, C _6-10 arylene groups). It is. The preferred group R ¹ is an arylene group, and among the arylene groups, asymmetric arylene groups such as a 1,2-phenylene group (o-phenylene group) and a 1,3-phenylene group (m-phenylene group) are preferable. The reason is not clear, but when a polycarbonyl compound having an asymmetric arylene group is used compared to a symmetric arylene group (such as 1,4-phenylene group), the compound of the present invention can be efficiently converted into a cyclic acetal or high molecular weight compound. It may be easy to make it.

The groups R ^2a and R ^{2b in the} formula (1) (which may be simply referred to as R ² collectively) usually correspond to the acyl group of a carbonyl compound (especially a polycarbonyl compound). Therefore, when the acyl group of the carbonyl compound is a formyl group (aldehyde group), R ^2a or R ^2b is a hydrogen atom, and when the acyl group of the polycarbonyl compound is an acyl group other than the formyl group (ketone group), R ^2a or R ^2b is a group corresponding to an acyl group (a group obtained by removing a carbonyl group from an acyl group or a ketone group).

Examples of the substituent represented by the groups R ^2a and R ^2b include a hydrocarbon group {for example, an aliphatic hydrocarbon group [for example, an alkyl group (for example, a methyl group, an ethyl group, an n-propyl group, C _1-20 such as isopropyl group, n-butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group, dodecyl group, octadecyl group An alkyl group, preferably a C _1-10 alkyl group, more preferably a C _1-8 alkyl group, etc.), a cycloalkyl group (eg, a C _5-10 cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, preferably C _5-8, such as a cycloalkyl group), an aralkyl group (e.g., benzyl group, _{C 6-10} aryl _{-C 1-4} such as phenethyl Saturated aliphatic hydrocarbon group such as alkyl group and the like); an alkenyl group (e.g., vinyl group, 1-propenyl group, allyl group, 1-butenyl, 2-butenyl, _{C 2-20} alkenyl such as 3-butenyl A group, preferably a C _2-10 alkenyl group, more preferably a C _2-6 alkenyl group), an alkadienyl group (eg, a C _4-10 alkadienyl group such as 2,7-octadienyl group), an aryl-alkenyl group (eg, 1-phenylvinyl group, aryl-C _2-10 alkenyl group such as 1-phenethyl-3-butenyl group, preferably C _6-10 aryl-C _2-6 alkenyl group) ], Aromatic hydrocarbon groups [e.g., aryl groups (e.g., C _6-10 aryl groups such as phenyl groups, etc.), etc.], etc. It is done.

Such groups R ^2a and R ^2b (or a hydrocarbon group) may have a substituent. Examples of the substituent include the same substituents as those exemplified in the section of R ¹ . The number of substituents can also be selected from the same range as R ¹ . Specific examples of the hydrocarbon group having a substituent include a substituent having a halogen atom [for example, a haloalkyl group (for example, a haloC _1-20 alkyl group such as iodomethyl group, trichloromethyl group, chloropentyl group, etc., preferably halo A hydrocarbon group substituted with a halogen atom such as a C _1-10 alkyl group, more preferably a halo C _1-6 alkyl group], a substituent having an alkoxy group [eg, an alkoxyalkyl group (eg, a 2-methoxypropyl group) C _1-10 alkoxy C _1-10 alkyl group such as 2-ethoxypropyl group, 2-isopropoxypropyl group, preferably C _1-6 alkoxy C _1-6 alkyl group, more preferably C _1-4 alkoxy C _1-4 alkyl group), aralkyloxy group (e.g., benzyloxy ethyl group, Baie Hydrocarbon group an alkoxy group substituted such as _{C 6-10} aryl _{C 1-4} alkoxy _{C 1-10} alkyl group), such as Gilles propyl group, a substituent having a nitro group [e.g., nitroaryl group (e.g., A nitro group having a nitro group such as a nitro C _6-10 aryl group such as a nitrophenyl group].

Representative groups R ^2a and R ^2b include a hydrogen atom, a hydrocarbon group (such as an alkyl group), and the like. Preferred groups R ^2a and R ^2b are hydrogen atoms.

In the groups R ^{3 to} R ⁵ of the formula (1), examples of the substituent include a hydrocarbon group {eg, an aliphatic hydrocarbon group [eg, an alkyl group (eg, a methyl group, an ethyl group, a propyl group, an isopropyl group] A C _1-10 alkyl group such as a group), a cycloalkyl group (eg a C _5-8 cycloalkyl group such as a cyclohexyl group), an aralkyl group (eg a C _6-10 aryl-C such as a benzyl group). Saturated alkyl hydrocarbon group such as _1-4 alkyl group); unsaturated aliphatic hydrocarbon group such as alkenyl group (eg, C _1-10 alkenyl group such as vinyl group, propenyl group)], aromatic hydrocarbon group [for example, an aryl group (e.g., a _{C 6-10} aryl group such as phenyl group), etc.], etc.}, an oxygen atom-containing group [e.g., a hydroxyl group, a carboxyl group, Sill group (formyl group, a C _1-4 acyl group such as acetyl group), alkoxycarbonyl groups (e.g., C _1-4 alkoxy such as methoxy carbonyl group - such as a carbonyl group), etc.], nitrogen-containing group [e.g., Nitro group, cyano group, amino group, substituted amino group (for example, mono- or dialkylamino group such as N, N-dimethylamino group, etc.), halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.) Etc.

The groups R ^{3 to} R ⁵ may be groups having a substituent (second substituent) in addition to these substituents (first substituent). For example, the groups R ^{3 to} R ⁵ may be a hydrocarbon group (for example, an alkyl group) substituted with an oxygen atom-containing group, a nitrogen atom-containing group, a halogen atom, or the like. The number of second substituents may be, for example, about 1 to 8, preferably 1 to 6, and more preferably about 1 to 4.

The group R ³ or R ⁴ and the group R ⁶ may be bonded to each other to form a ring [or the group R ³ or R ⁴ and the group R ⁶ are bonded to each other to form a divalent group ( For example, an alkylene group such as a methylene group, an ethylene group, a trimethylene group, or a tetramethylene group, preferably a C _1-6 alkylene group, more preferably a C _2-4 alkylene group)] may be formed. Examples of such a ring include an oxacycloalkane ring (for example, an oxaC _3-8 cycloalkane ring such as an oxacyclopentane ring and an oxacyclohexane ring, preferably an oxaC _4-6 cycloalkane ring). . Such an oxacycloalkane ring (or divalent group) may also have a second substituent.

Typical groups R ^{3 to} R ⁵ include a hydrogen atom, a hydrocarbon group [for example, a saturated aliphatic hydrocarbon group such as an alkyl group (such as a methyl group)] and the like. Representative groups R ³ and R ⁴ also include ring groups that are bonded to group R ⁶ to form an oxacycloalkane ring. Preferred groups R ^{3 to} R ⁵ are a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom.

The group R ⁶ of the formula (1) usually corresponds to a group bonded to an ether group of a vinyl ether compound (or a group obtained by removing a vinyloxy group from a vinyl ether compound), as will be described later. Therefore, the substituent represented by the group R ⁴ in the formula (1) is not particularly limited as long as it is a group (group that can be introduced) existing as a group bonded to the ether group of such a vinyl ether compound, For example, hydrocarbon group {for example, aliphatic hydrocarbon group [for example, alkyl group (for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, pentyl group , A hexyl group, an octyl group, a 2-ethylhexyl group, a dodecyl group, an octadecyl group and the like, a C _1-20 alkyl group, preferably a C _1-10 alkyl group, more preferably a C _1-8 alkyl group, particularly C _2-6. Alkyl group etc.), cycloalkyl group (for example, C _5-10 cycloalkyl group such as cyclopentyl group, cyclohexyl group, preferably C _5-8 cycl. A saturated aliphatic hydrocarbon group such as a C _6-10 aryl-C _1-4 alkyl group such as a benzyl group or a phenethyl group; an alkenyl group such as a vinyl group, 1- C _2-20 alkenyl group such as propenyl group, allyl group, 1-butenyl group, 2-butenyl group, preferably C _2-10 alkenyl group, more preferably C _2-6 alkenyl group), alkadienyl group (for example, 2 , 7-octadienyl group, C _4-10 alkadienyl group), aryl-alkenyl group (for example, aryl-C _2-10 alkenyl group such as 1-phenylvinyl group, 1-phenethyl-3-butenyl group, preferably C _6-10 an aryl _{-C 2-6} alkenyl group) unsaturated aliphatic hydrocarbon group such as, an aromatic hydrocarbon group [e.g. An aryl group (e.g., _{C 6-10,} such as an aryl group such as a phenyl group), etc., etc.]}, carbonyl group-containing group {for example, an acyl group [for example, an alkanoyl group (e.g., formyl group, acetyl group, n- propanoyl group, C _1-20 alkanoyl group such as isopropanoyl group, n-butanoyl group, isobutanoyl group, hexanoyl group, octanoyl group, pentadecanoyl group, etc., preferably C _1-10 alkanoyl group, more preferably C _2-6 alkanoyl group Etc.), an aroyl group (for example, a C _7-11 aroyl group such as a benzoyl group) and the like], an alkoxycarbonyl group (eg, a C _1-4 alkoxy-carbonyl group such as a methoxycarbonyl group) and the like}. .

The group R ⁶ includes, in addition to these substituents (first substituent), a substituent (second substituent) [for example, a hydroxyl group in addition to the above-exemplified substituents such as a hydrocarbon group and an acyl group. An alkoxy group [for example, a C _1-10 alkoxy group such as a methoxy group, an ethoxy group, or a propoxy group, preferably a C _1-6 alkoxy group, more preferably a C _1-4 alkoxy group; a benzyloxy group, a phenethyloxy group, etc. An aralkyloxy group (for example, a C _6-10 aryl C _1-4 alkoxy group)], a hydroxy (poly) alkoxy group {for example, a 2- (2-hydroxyethoxy) group, 2- [2- (2-hydroxy hydroxy, such as ethoxy) ethoxy] group _{(poly) C 2-6} alkoxy groups, preferably hydroxy mono- to hexa _{C 2-4} alkoxy group, more preferably Etc. hydroxy mono- to tetra C _2-3 alkoxy group}, a carboxyl group, (meth) acryloyl group (or methacryloyloxy group), a nitro group, a cyano group, an amino group, a substituted amino group (e.g., N, N-dimethyl A mono- or dialkylamino group such as an amino group) or a group having a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.).

  Such a second substituent is bonded (or substituted) to the first substituent through an appropriate linking group (for example, an ether group, an alkylene group, a (poly) oxyalkylene group, etc.). Also good.

Representative examples of such further substituted group R ⁶ include, for example, a substituent having a halogen atom [for example, a haloalkyl group (for example, a haloC _1-20 alkyl group such as a 2-chloroethyl group, preferably Is a hydrocarbon group substituted with a halogen atom such as a halo C _1-10 alkyl group, more preferably a halo C _1-6 alkyl group], a substituent having a hydroxyl group {eg, a hydroxyalkyl group (eg, 2-hydroxy Hydroxy C _2-20 alkyl group such as ethyl group, 2-hydroxypropyl group, 4-hydroxybutyl group, hydroxyhexyl group, preferably hydroxy C _2-10 alkyl group, more preferably hydroxy C _2-4 alkyl group), Hydroxy (poly) alkoxyalkyl groups [eg 2- (2-hydroxyethoxy) Hydroxy (poly) C _2-6 alkoxy C _2-6 alkyl group such as ethyl group, 2- [2- (2-hydroxyethoxy) ethoxy] ethyl group, preferably hydroxy mono to hexa C _2-4 alkoxy C _2- A hydrocarbon group having a hydroxyl group such as a _4- alkyl group, more preferably a hydroxymono to tetra-C _2-3 alkoxy C _2-3 alkyl group], a substituent having an alkoxy group {for example, an alkoxyalkyl group (for example, C _1-20 alkoxy C _2-20 alkyl group such as 2-methoxyethyl group, preferably C _1-10 alkoxy C _2-10 alkyl group, more preferably C _1-4 alkoxy C _2-4 alkyl group), alkoxy (Poly) alkoxyalkyl group [for example, 2- (2-methoxyethoxy) ethyl group, 2- [2 (2-methoxyethoxy) _{C 1-20} alkoxy _{(poly) C 2-6} alkoxy _{C 2-6} alkyl group such as ethoxy] ethyl group, preferably a _{C 1-10} Arukokishimono to hexa _{C 2-4} alkoxy _{C 2- 4} alkyl groups, more preferably C _1-4 alkoxymono to tetra C _2-3 alkoxy C _2-3 alkyl groups etc.] and other hydrocarbon groups having an alkoxy group (alkyl groups etc.)], polymerizable groups (eg A substituent having a (meth) acryloyl group, cinnamoyl group or the like (or a polymerizable group, for example, a (meth) acryloyloxyalkyl group (for example, a (meth) acryloyloxy C ₂ such as a 2- (meth) acryloyloxyethyl group). _-20 alkyl groups, preferably (meth) acryloyloxy C _2-10 alkyl groups, more preferably ( (Meth) acryloyloxy _C2-4 alkyl group), (meth) acryloyloxy (poly) alkoxyalkyl group [for example, (meth) acryloyloxy (poly) such as 2- (2- (meth) acryloyloxyethoxy) ethyl group C _2-6 alkoxy C _2-6 alkyl group, preferably (meth) acryloyloxy mono to hexa C _2-4 alkoxy C _2-4 alkyl group, more preferably (meth) acryloyloxy mono to tetra C _2-3 alkoxy A hydrocarbon group having a (meth) acryloyloxy group such as a C _2-3 alkyl group]; a cinnamoyloxyalkyl group (for example, a cinnamoyloxy C _2-4 alkyl group such as a 2-cinnamoyloxyethyl group), etc. Having a polymerizable group such as a hydrocarbon group having a cinnamoyloxy group Hydrocarbon group}, and the like.

Further, as described above, the group R ⁶ may be bonded to the group R ³ or R ⁴ to form a ring.

A representative group R ⁶ includes a hydrocarbon group (a hydrocarbon group which may be polymerizable). Preferred groups R ⁶ include saturated aliphatic hydrocarbon groups [eg, alkyl groups (eg, C _2-10 alkyl groups, preferably C _3-6 alkyl groups), haloalkyl groups, hydroxyalkyl groups, hydroxy (poly) Non-polymerizable hydrocarbon groups such as an alkoxyalkyl group, an alkoxyalkyl group, an alkoxy (poly) alkoxyalkyl group, a cycloalkyl group and the like] are included. Among these, in particular, in terms of polymerization reactivity, a secondary or tertiary hydrocarbon group (a hydrocarbon in which the carbon atom bonded to the oxygen atom (—O—) is a secondary or tertiary carbon atom) Group), for example, secondary or tertiary alkyl group (for example, secondary or tertiary C _3-10 alkyl group such as isopropyl group, s-butyl group, t-butyl group, etc., preferably secondary or tertiary group) Secondary or tertiary saturated aliphatic such as a tertiary C _3-6 alkyl group), a cycloalkyl group (eg, a C _5-10 cycloalkyl group such as a cyclohexyl group, preferably a C _5-8 cycloalkyl group). A hydrocarbon group is preferred. Therefore, the multimeric compound of the present invention is a unit (non-polymerized) in which the group R ⁶ in the formula (1) is a non-polymerizable hydrocarbon group (particularly a secondary or tertiary saturated aliphatic hydrocarbon group). Sex unit).

The preferred group R ⁶ also includes a polymerizable substituent (polymerizable group). In the above formula (1), a compound having a unit in which the group R ⁶ is a polymerizable substituent (for example, a group having an α, β-ethylenically unsaturated bond) is crosslinked using a polymerizable group. Because the structure can be formed (or the molecular weight can be increased), high adhesion can be efficiently imparted to the adherend. Further, as described above, since the cyclic acetal structure is usually formed by the acyl group of the carbonyl compound and the vinyl group portion of the vinyl ether compound, the group R ⁶ is a 1-alkenyl group (such as a vinyl group). In some cases, the cyclic acetal compound (particularly a multimeric compound) may be a compound in which a unit represented by the formula (1) is further bonded via a 1-alkenyl group as the substituent R ⁶ . In such a case, the cyclic acetal compound may form a branched or branched network structure, and the adhesiveness can be improved by increasing the molecular weight as in the case where the polymerizable group itself forms a crosslinked structure. There is.

From such a viewpoint, as described later, the cyclic acetal compound is a substituent (or a polymerizable group or a polymerizable substituent such as a polymerizable hydrocarbon) in which the group R ⁶ is polymerizable in the formula (1). Group (unit represented by the formula (1b)).

As such a polymerizable group (polymerizable substituent) R ⁶ , a polymerizable hydrocarbon group (polymerizable hydrocarbon group), for example, an unsaturated hydrocarbon group {for example, an unsaturated aliphatic hydrocarbon group) Group [for example, alkenyl group (for example, C _2-10 alkenyl group such as vinyl group, allyl group, preferably C _2-6 alkenyl group), alkadienyl group, aryl-alkenyl group, etc.]}, polymerizable group Hydrocarbon group having {for example, (meth) acryloyloxyalkyl group [for example, (meth) acryloyloxy C _2-10 alkyl group, preferably (meth) acryloyloxy C _2-4 alkyl group], (meth) acryloyloxy ( Poly) alkoxyalkyl group [for example, (meth) acryloyloxymono thru | or tetra _C2-4 alkoxy _C2-4 alkyl group etc. ] Or the like (hydrocarbon groups (aliphatic (especially saturated aliphatic) hydrocarbon groups such as alkyl groups)) having a polymerizable group (such as (meth) acryloyloxy group)}. Among these, an alkenyl group and a hydrocarbon group having a (meth) acryloyloxy group (particularly an alkyl group) are preferable, and a hydrocarbon group having a (meth) acryloyloxy group is particularly preferable.

(Structure and properties of cyclic acetal compound)
Among the cyclic acetal compounds, the multimeric compound has a unit represented by the formula (1) as a repeating unit. Such repeating units may be the same unit or different units. In addition, when it has different units, the cyclic acetal compound is in a form in which different units (specifically, units in which at least one of groups R ^{1 to} R ⁶ are different in formula (1)) are bonded to each other (in one polymer molecule). B) may have a plurality of different units, or may be in the form of a mixture of multimeric compounds having different units. In the former case, that is, in the case of a copolymer (copolymer) containing different units, the form of the multimeric compound (copolymerization form) is any of a random copolymer, a block copolymer, an alternating copolymer, etc. There may be.

The multimeric compound is a unit (non-polymerizable) in which (A) the group R ⁶ in the formula (1) is a non-polymerizable substituent (for example, a non-polymerizable hydrocarbon group) according to the desired required performance. Unit (sometimes referred to as unit (1a)) (comprising only one or two or more non-polymerizable units). (B) In the formula (1), the group R ⁶ is polymerized. A compound (consisting only of one or more polymerizable units) consisting only of units (polymerizable units, sometimes referred to as units (1b)) which are substituents having a property (for example, polymerizable hydrocarbon groups). Alternatively, it may be a compound having a combination of (C) a non-polymerizable unit (one or two or more non-polymerizable units) and a polymerizable unit (one or two or more polymerizable units).

In particular, in order to improve adhesion and the like, the multimeric compound may have at least a polymerizable unit (unit represented by the formula (1b)) (that is, the above (B) or (C ), More preferably, from the viewpoint of achieving a good balance between adhesion and decomposability, a non-polymerizable unit (unit represented by the formula (1a)) and a polymerizable unit are used. You may have in combination (that is, the aspect of (C) may be sufficient). From the viewpoint of polymerizability, the multimeric compound may have at least a unit in which R ⁶ is a secondary or tertiary saturated aliphatic hydrocarbon group.

  When the nonpolymerizable unit (1a) and the polymerizable unit (1b) are combined, these ratios in the multimeric compound are the former / the latter (molar ratio) = 99.9 / 0.1 to 10/90 ( For example, it can be selected from the range of about 99.5 / 0.5 to 20/80), for example, 99/1 to 25/75 (for example, 98/2 to 30/70), preferably 97/3 to 35 / 65 (for example, 95/5 to 40/60), more preferably 93/7 to 45/55 (for example, 90/10 to 50/50), particularly 88/12 to 55/45 (for example, 85/15 to 60/40, preferably 83/17 to 65/35, more preferably 80/20 to 70/30), and usually 99/1 to 40/60 (for example, 95/5 to 45/55). ) Degree.

In addition, the structure of the multimeric compound may usually be a chain structure (linear structure), but as long as it has the unit represented by the formula (1) as a repeating unit, it is branched. It may be a structure or a network structure (or a branched structure or a network structure may be included in a part of the structure of the multimeric compound). As described above, in the branched structure or network structure, when the group R ¹ further has an acyl group as a substituent (when the polycarbonyl compound has three or more acyl groups), the group R ⁶ has a 1-alkenyl group. (When the vinyl ether compound is a divinyl ether compound) or when the group R ⁶ is a polymerizable substituent, it can be introduced into the multimeric compound.

  As will be described later, the multimeric compound usually has two polycarbonyl compounds (specifically, one acyl group of one polycarbonyl compound and one acyl group of the other polycarbonyl compound) and one vinyl ether system. A cyclic acetal structure is formed by reaction with the compound, and further, it is obtained by repeatedly forming a cyclic acetal structure by reacting the remaining acyl group of the polycarbonyl compound with another vinyl ether compound.

  Therefore, the terminal group of the multimeric compound may be a group derived from a polycarbonyl compound raw material (that is, an acyl group). Specifically, the structure of the multimeric compound (particularly, the structure when the polycarbonyl compound used as a raw material is a compound having two acyl groups) may be a structure represented by the following formula (A).

(In the formula, n represents an integer of 2 or more, and R ¹ , R ^2a , R ^2b , R ³ , R ⁴ , R ⁵ , and R ⁶ are the same as described above.)
If necessary, an acyl group is a terminal group (group ^R 2a CO- and / or groups ^R 2b CO-) may be modified. In the reaction, a small amount of a monocarbonyl compound (for example, monoaldehyde) may be used to obtain a multimeric compound having no acyl group at the terminal.

  The multimeric compound may contain other units (constituent units) as long as it contains at least the unit represented by the formula (1) as a repeating unit. In addition, the multimeric compound should just have the unit represented by Formula (1) as a repeating unit (namely, it has 2 or more in a molecule | numerator), and is adjacent to the unit represented by Formula (1) (bond | coupled). The unit is normally a unit represented by the formula (1), but may be another unit.

  The molecular weight of the cyclic acetal compound (particularly the multimeric compound) can be selected, for example, from the range of 400 or more (for example, 450 to 100,000) in terms of number average molecular weight (Mn), 500 or more (for example, 550 to 50,000), preferably It may be 600 or more (for example, 650 to 30000), more preferably about 700 or more (for example, 750 to 10000), and usually about 500 to 7000 (for example, 600 to 5000, preferably 700 to 3000). Also good.

  The weight average molecular weight (Mw) of the cyclic acetal compound (particularly the multimeric compound) can be selected from the range of 600 or more (for example, 650 to 100,000), for example, 700 or more (for example, 750 to 50000), preferably It may be 800 or more (for example, 850 to 30000), more preferably about 900 or more (for example, 950 to 15000), and usually 700 to 10,000 (for example, 750 to 7000, preferably 800 to 5000, more preferably 850). ˜4000).

  The molecular weight distribution (Mw / Mn) of the cyclic acetal compound (particularly the multimeric compound) is, for example, 1 to 5, preferably 1.1 to 3, and more preferably 1.2 to 2.5 (for example, 1 About 3 to 2.2).

  The molecular weight and molecular weight distribution can be measured, for example, as a value in terms of polystyrene using GPC (gel permeation chromatography).

  The multimeric compound may be an oligomer such as a dimer (a compound having two units represented by the formula (1)), a trimer, or a polymer. In the multimeric compound, the average number of units represented by the formula (1) (the average number of repeating units, for example, the number corresponding to n in the formula (A)) is 2 or more (for example, 2 to 2 5000), for example, 2 to 3000 (eg, 2.2 to 1000), preferably 2.5 to 800 (eg, 2.5 to 500), more preferably 2.7 to 300 (eg, 3 to 200) or about 2 to 100 (e.g. 2 to 50, preferably 2.2 to 30, more preferably 2.5 to 20, especially 3 to 10). Good.

  The cyclic acetal compound (or the adhesive of the present invention) may be liquid (including viscous liquid) or solid at normal temperature (for example, 15 to 25 ° C.), but is usually solid. May be.

  The cyclic acetal compound (or the multimeric compound or the adhesive of the present invention) is excellent in heat resistance. For example, the 5% by weight reduction temperature (5% by weight thermal decomposition temperature) is 100 ° C. or higher (for example, 120 to 400 ° C.). , Preferably 130 ° C. or higher (eg 140 to 350 ° C.), more preferably 150 ° C. or higher (eg 160 to 320 ° C.), 180 ° C. or higher (eg 190 to 400 ° C., preferably 200 ° C.) Above).

  The cyclic acetal compound (or the adhesive of the present invention) has adhesiveness (or tackiness). The adhesiveness of the cyclic acetal compound may be possessed by the liquid cyclic acetal compound (for example, it may be expressed by a viscous cyclic acetal compound at room temperature). , It may have thermal adhesiveness (hot melt adhesiveness).

  The cyclic acetal compound (or the adhesive of the present invention) is viscous (or viscous) at a predetermined temperature despite being solid (non-adhesive solid) at normal temperature (for example, 15 to 25 ° C.). In many cases, it is hot melt adhesive. For example, the bonding temperature [hot melt bonding temperature (temperature at which hot melt bonding is possible)] of the cyclic acetal compound (or the adhesive of the present invention) is 70 to 180 ° C, preferably 80 to 170 ° C, more preferably 90 to 90 ° C. It may be about 160 ° C, particularly about 100 to 150 ° C, and usually about 80 to 150 ° C (for example, 90 to 140 ° C).

  At the bonding temperature (hot melt bonding temperature), the viscosity of the cyclic acetal compound (or the adhesive of the present invention) is, for example, about 0.01 to 10,000 Pa · s, preferably about 0.1 to 10,000 Pa · s. Also good. The viscosity can be measured with a rheometer, for example.

  The cyclic acetal compound is usually soluble in a general-purpose solvent. Therefore, it is also suitable for use as a coating application. Examples of such solvents include ester solvents (for example, acetate esters such as ethyl acetate, butyl acetate, and propylene glycol monomethyl ether monoacetate), ketone solvents (for example, chain ketones such as acetone; cyclohexanone, and the like. Cyclic ketones), ether solvents (eg, chain ethers such as propylene glycol monomethyl ether and diethylene glycol dimethyl ether; cyclic ethers such as dioxane and tetrahydrofuran), aromatic solvents (eg, aromatic carbonization such as toluene and xylene) Hydrogen), halogenated solvents (for example, haloalkanes such as dichloromethane and chloroform), alcoholic solvents (for example, alkanols such as methanol, ethanol, isopropanol, and butanol), nito Le solvents (e.g., acetonitrile, and benzonitrile), nitro solvents (e.g., nitrobenzene etc.) and the like.

  Further, the cyclic acetal compound has a characteristic that it is easily decomposed by an acid. Therefore, the compound of the present invention can also be used as an acid-responsive material as will be described later.

(Method for producing cyclic acetal compound)
The cyclic acetal compound is not particularly limited, but is usually a compound represented by the following formula (2) [carbonyl compound, particularly a polycarbonyl compound (a compound having at least two carbonyl groups)] and the following formula (3). It can be obtained by reacting the compound (vinyl ether compound) represented.

(In the formula, p is 1 or 2, R ² is R ^2a or R ^2b , and R ^{1 to} R ⁶ are the same as above. However, when p is 1, R ² is R ^2a and p is 2. Sometimes two R ² are R ^2a and R ^2b )
In the compound represented by the formula (3), the substitution position (geometric isomerism) of R ³ , R ⁴ , R ⁵ and (OR ⁶ ) may be either cis or trans.

The compound represented by the above formula (2) (carbonyl compound) may be a compound having at least one or two acyl groups (group R ² CO—), and three or more acyl groups as described above. It may be a compound having The compound having two or more acyl groups corresponds to the compound represented by the following formula (2A), and the compound having three or more acyl groups is p in the above formula (2), This corresponds to the case where the group R ¹ has an acyl group as a substituent.

(In the formula, R ¹ , R ^2a and R ^2b are the same as above.)
Typical examples of the compound represented by the formula (2) include aliphatic polyaldehydes [for example, C _2-14 such as alkane dial (eg, glyoxal, glutaraldehyde (1,5-pentane dial)). Aliphatic dialdehydes such as alkane _dials , preferably C _{2-12 alkane} dials, more preferably C _2-8 alkane diar], aromatic polyaldehydes [eg diformyl arenes (eg phthalaldehyde, isophthal An aromatic dialdehyde such as diformyl C _6-14 arene, preferably diformyl C _6-12 arene, more preferably diformyl C _6-10 arene) such as aldehyde and terephthalaldehyde (in formula (2)) Compounds wherein R ² is a hydrogen atom, in particular dia Rudehydric compounds or diformyl compounds); corresponding to these polyaldehyde compounds, compounds in which formyl groups are substituted with acyl groups (acyl groups other than formyl groups) (for example, polyketone compounds); corresponding to these polyaldehyde compounds or polyketone compounds Monoaldehyde compounds {eg, aliphatic monoaldehydes [eg, alkanals (eg, C _1-14 alkanals such as formaldehyde, acetaldehyde, preferably C _2-12 alkanals, more preferably C _2-8 alkanals)] Etc.], aromatic monoaldehydes [for example, formyl arenes (for example, formyl C _6-10 arenes such as benzaldehyde, etc.), etc.] or monoketone compounds. Among these, preferred aromatic polyaldehydes include asymmetric aromatic polyaldehydes (for example, compounds in which a formyl group such as phthalaldehyde or isophthalaldehyde is substituted at an asymmetric position with respect to the arene ring). If an asymmetric aromatic polyaldehyde is used, a side reaction can be suppressed efficiently, or a multimeric compound can be obtained efficiently.

  The compounds represented by the formula (2) may be used alone or in combination of two or more.

The compound represented by the formula (3) is a vinyl ether compound (1-alkenyl ether compound), and the group R ⁶ may be a polymerizable group as described above. Typical examples of the compound represented by the formula (3) include alkyl vinyl ethers (for example, methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, t-butyl vinyl ether, C _1-20 alkyl-vinyl ethers such as sec-butyl vinyl ether, hexyl vinyl ether, octyl vinyl ether, 2-ethylhexyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether, preferably C _1-10 alkyl-vinyl ether, more preferably C _1-6 alkyl- Vinyl ether), haloalkyl vinyl ethers (halo C _1-20 alkyl-vinyl ethers such as 2-chloroethyl vinyl ether) Ter, preferably halo C _1-10 alkyl-vinyl ether, more preferably halo C _1-6 alkyl-vinyl ether), hydroxyalkyl vinyl ethers (eg, hydroxy C _2-10 such as 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether). Alkyl-vinyl ethers, more preferably hydroxy C _2-6 alkyl-vinyl ethers), polyalkylene glycol monovinyl ethers (eg poly C _2-4 alkylene glycol monovinyl ethers such as diethylene glycol monovinyl ether, triethylene glycol vinyl ether), polyalkylene glycol mono alkyl monovinyl ether (e.g., poly C _2-4 alkylene such as diethylene glycol monomethyl monovinyl ether Glycol mono _{C 1-10} alkyl mono-ether), a cycloalkyl vinyl ether (e.g., _{C 5-10} cycloalkyl such as cyclohexyl vinyl ether - ether, preferably _{C 5-8} cycloalkyl - vinyl ether), aralkyl ethers (e.g., benzyl R ⁶ such as C _6-10 aryl C _1-4 alkyl-vinyl ether such as vinyl ether and phenethyl vinyl ether), alkyl isopropenyl ether (eg, C _1-10 alkyl-isopropenyl ether such as methyl isopropenyl ether) is not polymerized A compound which is a polymerizable substituent (for example, non-polymerizable hydrocarbon group); an alkenyl vinyl ether (for example, divinyl ether, 1-propenyl vinyl ether, 2-propenyl vinyl ether). Ether, _{C 2-10} alkenyl such as 1-butenyl vinyl ether - ether), (meth) acryloyloxy (poly) alkoxyalkyl - vinyl ethers [e.g., 2- (2- (meth) acryloyloxy) ethyl - ether such as (Meth) acryloyloxy (poly) C _2-6 alkoxy C _2-6 alkyl-vinyl ether, preferably (meth) acryloyloxy mono to hexa C _2-4 alkoxy C _2-4 alkyl-vinyl ether, more preferably (meth) A compound in which R ⁶ is a polymerizable group (or a polymerizable substituent such as a polymerizable hydrocarbon group), such as acryloyloxymono to tetra-C _2-3 alkoxy C _2-3 alkyl-vinyl ether, etc .; 2-oxacyclohexene (For example, 2-oxacyclo Compounds in which R ³ or R ⁴ and R ⁶ form a ring such as 2-oxaC _3-8 cycloalkene such as pentene and 2-oxacyclohexene, preferably 2-oxaC _4-6 cycloalkene) (cyclic vinyl ether) System compounds) and the like.

  In particular, the compound represented by the formula (3) may be a solid compound at normal temperature (for example, 15 to 25 ° C.).

The compounds represented by the formula (3) may be used alone or in combination of two or more. In particular, in formula (3), R ⁶ is a non-polymerizable substituent (sometimes referred to as a non-polymerizable compound, compound (3A), etc. That is, a compound represented by the following formula (3A)); By combining with a compound in which R ⁶ is a polymerizable substituent (polymerizable compound, compound (3B), etc., that is, a compound represented by the following formula (3B)), as described above, A multimeric compound having a polymerizable unit (1a) and a polymerizable unit (1b) can be obtained.

(Wherein R ³ , R ⁴ , R ⁵ , R ^6a and R ^6b are the same as above).
When obtaining such a multimeric compound, the ratio of the compound (3A) and the compound (3B) can be selected from the same range as the ratio of the unit in the multimeric compound, and the former / the latter (molar ratio) = 99. 9 / 0.1 to 10/90 (for example, 99.5 / 0.5 to 20/80), for example, 99/1 to 25/75 (for example, 98/2 to 30/70), preferably 97 / 3 to 35/65 (for example, 95/5 to 40/60), more preferably 93/7 to 45/55 (for example, 90/10 to 50/50), particularly 88/12 to 55/45 (for example, 85/15 to 60/40, preferably 83/17 to 65/35, more preferably 80/20 to 70/30), and usually 99/1 to 40/60 (for example, 95/5). About 45/55).

  The cyclic acetal structure is formed by a reaction between two acyl groups and a vinyl group (1-alkenyl group). Therefore, in the reaction, the compound represented by the formula (2) and the compound represented by the formula (3) are usually represented by the formula (3) with respect to 2 mol of the acyl group of the compound represented by the formula (2). ) [The vinyl group (or 1-alkenyl group adjacent to the ether group of the compound represented by the formula (3)] is, for example, 0.5 to 2 mol, preferably 0.7 to You may use it in the ratio used as 1.4 mol, More preferably 0.8-1.2 mol, Especially about 1 mol (for example, 0.9-1.1 mol) grade.

  When obtaining a multimeric compound, typically, for example, 0.5 mol of the compound represented by the formula (3) with respect to 2 mol of the compound represented by the formula (2) (dialdehyde compound, etc.) To 2 mol, preferably 0.7 to 1.4 mol, more preferably 0.8 to 1.2 mol, particularly about 1 mol (for example, 0.9 to 1.1 mol). May be.

The reaction may usually be performed in the presence of a catalyst. The catalyst is not particularly limited as long as it is a catalyst that acts in the formation reaction of the cyclic acetal structure. For example, a Lewis acid catalyst can be preferably used. Such a Lewis acid catalyst may be any of a hard acid, a soft acid, and an acid belonging to the intermediate in the principle of HSAB, but is a hard acid (a compound or complex of a hard acid and a hard base). In some cases, a cyclic acetal structure is formed and multimerization is likely to occur. Typical catalysts (Lewis acid catalysts) include aluminum catalysts [eg, alkylaluminum dihalides (eg, ethylaluminum dichloride (C ₂ H ₅ AlCl ₂ ), etc.), aluminum trihalides (eg, AlCl ₃ etc.), etc. aluminum halides, tin-based catalysts (e.g., tin halides such as SnCl _4), and the like. The catalysts may be used alone or in combination of two or more.

  The amount of the catalyst used is, for example, 0.01 to 30 mol (for example, 0.05 to 30 mol) with respect to 100 mol of the total amount of the compound represented by the formula (2) and the compound represented by the formula (3). 20 mol), preferably 0.1 to 15 mol (for example, 0.5 to 10 mol), more preferably about 0.7 to 10 mol (for example, 1 to 8 mol).

  The catalyst may be present (added) in the reaction system at a time, or may be present in the reaction system by stepwise addition.

In addition, you may perform reaction in presence of a polymerization inhibitor (thermal polymerization inhibitor, radical polymerization inhibitor) as needed. In particular, when a compound in which the group R ⁶ is a polymerizable group in the formula (3) is used, the polymerizable group is efficiently introduced into the multimeric compound by performing the reaction in the presence of a polymerization inhibitor. (Residual).

  Specific polymerization inhibitors include hydroquinone compounds (for example, hydroquinone, methylhydroquinone, 2,5-di-t-butylhydroquinone, 2,5-di-t-amylhydroquinone, etc.) and antioxidants. Or compounds known as stabilizers [eg phenolic compounds (or phenolic antioxidants such as hindered phenolic compounds), amine compounds (or amine antioxidants such as aromatic amines), Phosphorus compounds (or phosphorus antioxidants such as phosphite compounds and phosphine compounds), sulfur compounds (or sulfur antioxidants), quinoline compounds (or quinoline antioxidants), hindered amine compounds, etc. ] Etc. are mentioned. The polymerization inhibitors may be used alone or in combination of two or more.

  When the reaction is carried out in the presence of the polymerization inhibitor, the ratio of the polymerization inhibitor is, for example, on a weight basis with respect to the total amount of the compound represented by the formula (2) and the compound represented by the formula (3). 1 to 10000 ppm, preferably 10 to 5000 ppm, more preferably about 100 to 3000 ppm, and usually about 10 to 1000 ppm.

  The reaction may be performed in a solvent (in the presence of a solvent). The solvent is not particularly limited. For example, ether solvents (eg, chain ethers such as propylene glycol monomethyl ether and diethylene glycol dimethyl ether; cyclic ethers such as dioxane and tetrahydrofuran), aromatic solvents (eg, toluene, xylene) Aromatic hydrocarbons), halogen solvents (for example, haloalkanes such as dichloromethane and chloroform) and the like. The solvents may be used alone or in combination of two or more. In particular, ether solvents (for example, dioxane, tetrahydrofuran, etc.) may improve the catalytic activity of the Lewis acid catalyst because it acts as a Lewis base.

  When making it react in a solvent, the ratio (concentration) of the compound represented by the said Formula (2) and the compound represented by the said Formula (3) in a solvent (reaction liquid, reaction liquid mixture) is 0.1-. It may be about 50% by weight, preferably 0.5 to 30% by weight, more preferably about 1 to 20% by weight.

  Although reaction temperature is not specifically limited, For example, -70 degreeC or more (for example, -70 to 80 degreeC), Preferably it is -50 to 70 degreeC (for example, -40 to 60 degreeC), Preferably it is -30 degreeC It may be about -50 ° C, more preferably about -20 ° C to 40 ° C (for example, -20 to 20 ° C), and usually about -70 ° C to 50 ° C. In the present invention, a cyclic acetal structure (particularly a multimeric compound) can be formed even under extremely low temperature conditions.

  The reaction may be performed under an atmosphere of inert gas (such as helium, nitrogen, argon) or under circulation. Further, the reaction may be performed under normal pressure, increased pressure, or reduced pressure. The reaction is preferably performed in the absence of moisture (proton source). However, in the present invention, a cyclic acetal compound can be obtained even under an extremely low moisture concentration (for example, 5 ppm or less). .

  A multimeric compound is obtained as a product as described above. The product may be separated and purified by a separation method (separation method) such as filtration, concentration, reprecipitation, extraction, crystallization (recrystallization, etc.).

[Adhesive and bonding method]
The adhesive only needs to contain the cyclic acetal compound (or be composed of the cyclic acetal compound), and may contain other components. In addition, you may combine the cyclic acetal compound which comprises an adhesive agent 1 type (s) or 2 or more types. In particular, the adhesive may contain an acid generator in addition to the cyclic acetal compound. By including such an acid generator, adhesiveness (for example, hot melt adhesiveness) and decomposability by an acid can be imparted to the adhesive.

  As the acid generator, a thermal acid generator {an acid generator that generates an acid by heat, for example, a sulfonic acid-based thermal acid generator [for example, arenesulfonic acid esters (for example, benzoin tosylate, nitrobenzyl tosylate, etc.) Sulfonic acid esters, etc.], carboxylic acid-based thermal acid generators [for example, fatty acids (for example, citric acid, acetic acid, maleic acid, etc.) or salts thereof, aromatic carboxylic acids (for example, benzoic acid, phthalic acid, etc.) or their Salt, etc.], phosphoric acid-based thermal acid generator (for example, phosphoric acid, organic phosphate ester, etc.)}, photoacid generator and the like. The acid generators may be used alone or in combination of two or more.

  In addition, when combining a hot-melt-adhesive and a thermal acid generator, you may use suitably the thermal-acid generator which does not generate | occur | produce an acid at hot-melt-bonding temperature. A preferred acid generator is a photoacid generator. When a photoacid generator is used, even if it is a hot melt adhesive (adhesive property is exhibited at a predetermined temperature) cyclic acetal compound, the adhesive can be efficiently decomposed with an acid after being subjected to adhesion.

The photoacid generator is an acid generator that generates an acid upon irradiation with active light (for example, visible light, ultraviolet light, electron beam, X-ray, etc.). The photoacid generator may be an acid generator that generates an acid by heat. Representative active rays include visible rays, ultraviolet rays and the like. Typical photoacid generators include, for example, quinonediazide compounds, onium salts (for example, sulfonium salts, phosphonium salts, diazonium salts, iodonium salts, selenium salts), phenols, sulfonic acids or esters thereof, carboxylic acids or esters thereof. Etc. can be exemplified. Examples of the counter ion of the onium salt include borate (eg, BF ₄ ⁻ , B (C ₆ F ₅ ) ₄ ^—, etc.), phosphate (eg, PF ₆ ^— etc.), sulfonate (eg, CF ₃ SO _3). ^- etc.), antimonate (e.g., SbF ₆ ^-, etc.), and the anions such.

  Specific photoacid generators include, for example, quinonediazide compounds (for example, naphthoquinonediazide compounds), sulfonium salts [for example, alkylsulfonium salts (for example, trialkylsulfonium salts), arylsulfonium salts (for example, diarylsulfonium salts) , Triarylsulfonium salts, etc.], phosphonium salts [eg, arylphosphonium salts (eg, triarylphosphonium salts), etc.], diazonium salts (eg, aryldiazonium salts), iodonium salts [eg, aryliodonium salts (eg, Diaryliodonium salts)], selenium salts [eg aryl selenium salts (eg triaryl selenium salts)] phenols (eg phenol, resorcinol, pyrogallol) 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, etc.), sulfonic acids (eg, alkane sulfonic acids such as methane sulfonic acid, ethane sulfonic acid, propane sulfonic acid, butane sulfonic acid; benzene sulfonic acid, naphthalene sulfonic acid, etc. Arenesulfonic acid; camphorsulfonic acid, etc.) or esters thereof (eg, arenesulfonic acid esters). The photoacid generators may be used alone or in combination of two or more.

  The ratio of the acid generator is, for example, 0.01 to 20 parts by weight, preferably 0.1 to 15 parts by weight, and more preferably about 0.5 to 10 parts by weight with respect to 100 parts by weight of the cyclic acetal compound. May be.

The adhesive may contain a polymerization initiator as necessary. When a polymerizable cyclic acetal compound (for example, a compound in which R ⁶ is a polymerizable substituent in the formula (1)) and a polymerizable initiator are combined, an appropriate stage (for example, at the time of adhesion, after adhesion, etc.) Thus, a polymerization (crosslinking) reaction with a polymerizable substituent can be efficiently generated.

  As the polymerization initiator (radical polymerization initiator), any of thermal polymerization initiators and photopolymerization initiators (for example, benzoins, acetophenones, anthraquinones, thioxanthenes, thioxanthones, acridines, sulfides, etc.) It can be used. The polymerization initiators may be used alone or in combination of two or more. In particular, in the case of a hot melt adhesive, a thermal polymerization initiator may be suitably used because the hot melt adhesive can be efficiently bonded together with the polymerization.

  Examples of the thermal polymerization initiator include peroxides {for example, diacyl peroxides [for example, dialkanoyl peroxide (for example, lauroyl peroxide)), dialoyl peroxide (for example, benzoyl peroxide). Benzoyl toluyl peroxide, toluyl peroxide, etc.)], dialkyl peroxides (for example, di-t-butyl peroxide, dicumyl peroxide, etc.), peracid esters [t-butyl peracetate, t-butyl peroxide, etc. Oxyoctoate, percarboxylic acid alkyl ester such as t-butylperoxybenzoate, etc.]}, azo compounds {eg, azonitrile compounds [2,2′-azobis (2,4-dimethylvaleronitrile), 2,2 ′ -Azobis (isobutyronitrile), , 2′-azobis (2-methylbutyronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), etc.], azoamide compounds {2,2′-azobis {2-methyl- N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide} and the like}, azoamidine compounds {2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis [ 2- (2-imidazolin-2-yl) propane] dihydrochloride, etc.}, azoalkane compounds [2,2′-azobis (2,4,4-trimethylpentane), 4,4′-azobis (4-cyanopentane) Acid) etc.] etc.}. You may use a thermal-polymerization initiator individually or in combination of 2 or more types.

  The ratio of the polymerization initiator is, for example, 0.01 to 15 parts by weight (for example, 0.05 to 12 parts by weight), preferably 0.1 to 10 parts by weight, more preferably 100 parts by weight of the cyclic acetal compound. May be about 0.5 to 5 parts by weight.

  Moreover, the adhesive agent may contain the polymerization inhibitor (or polymerization inhibitor) as needed. By combining a polymerizable multimeric compound, a polymerization initiator, and a polymerization inhibitor (radical polymerization inhibitor), in the adhesive (or after bonding), excessive polymerization (crosslinking) of the cyclic acetal compound is suppressed and adhesion is improved. (Or heat resistance) and decomposability by an acid can be balanced. Examples of the polymerization inhibitor include the compounds exemplified in the method for producing the cyclic acetal compound (for example, hindered phenol compounds). The polymerization inhibitors may be used alone or in combination of two or more.

  The ratio of the polymerization inhibitor may be, for example, 1 to 10000 ppm, preferably 10 to 5000 ppm, more preferably about 100 to 3000 ppm, and usually about 10 to 1000 ppm based on the weight with respect to the multimeric compound. May be.

  The polymerizable composition may contain a conventional additive as required. Examples of such additives include pigments, colorants, thickeners, sensitizers, antifoaming agents, stabilizers, surfactants, antistatic agents, fillers, and the like. These additives may be used alone or in combination of two or more.

  The adhesive may be a solventless adhesive that does not contain a solvent, or may be an adhesive that contains a solvent, depending on the application. Examples of the solvent include alcohols (alkyl alcohols such as ethanol, propanol and isopropanol, glycols such as ethylene glycol and propylene glycol), hydrocarbons (for example, aromatic hydrocarbons such as toluene and xylene), halogens, and the like. Hydrocarbons (eg, methylene chloride, chloroform, etc.), ethers (eg, chain ethers such as diethyl ether, cyclic ethers such as dioxane, tetrahydrofuran, etc.), esters (eg, ethyl acetate, butyl acetate, etc.) ), Ketones (eg, chain ketones such as acetone, ethyl methyl ketone, and methyl isobutyl ketone, cyclic ketones such as cyclohexanone), glycol ethers (eg, ethylene glycol monomethyl ether, ethylene glycol). Glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, 3-methoxybutanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether), glycol Ether esters (for example, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, etc.), amides (N, N-dimethylformamide, N, N-dimethylacetamide, etc.), nitriles (acetonitrile, benzonitrile, etc.), N -Such as methylpyrrolidone Machine solvents. The solvents may be used alone or in combination of two or more.

  The ratio (concentration) of the cyclic acetal compound in the solvent can be selected depending on the application, and is, for example, 1 to 95% by weight (for example, 3 to 90% by weight), preferably 5 to 85% by weight (for example, 10 to 80%). % By weight), more preferably about 15 to 75% by weight (for example, 20 to 70% by weight).

  The properties of the adhesive of the present invention (in the case of an adhesive containing a solvent, the solid content of the adhesive) usually correspond to the properties of the multimeric compound. For example, the adhesive of the present invention may be liquid (including viscous liquid) or solid at normal temperature (for example, 15 to 25 ° C.), but may be usually solid. In addition, the adhesive of the present invention is usually often thermal adhesive (hot melt adhesive), and the viscosity (viscosity at 100 ° C.) of such an adhesive can be selected from the same range as described above.

  The adhesive of the present invention can be used as a powder if it is solid, or as a liquid if it is a coating liquid containing a solvent. Depending on the application, the adhesive can be molded into an appropriate shape and used. Also good. For example, the adhesive (or multimeric compound) of the present invention is often hot-melt adhesive or solid, as described above, and can be used as a sheet. The sheet-like adhesive can be used as an adhesive in the form of being laminated on an adherend.

  In the sheet-like adhesive, the sheet thickness can be appropriately selected depending on the application, but may be, for example, 1 to 300 μm (for example, 2 to 200 μm), preferably 5 to 100 μm, and more preferably about 10 to 80 μm. .

  Moreover, the adhesives (sheet-like adhesive etc.) of this invention can also be used as a laminated sheet laminated | stacked on the base material sheet as needed. The material of the base sheet is not particularly limited, and plastic “for example, olefin resin, polyester resin (polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc.), polyamide resin (nylon 6, nylon 66, nylon, etc.) 12), styrene resin (polystyrene, acrylonitrile-styrene copolymer, etc.), vinyl chloride resin (polyvinyl chloride, etc.), polycarbonate resin, polysulfone resin, polyphenylene ether resin, polyphenylene sulfide resin, polyvinyl alcohol. Resin, cellulose ester resin, etc.], glass, ceramics, metal, etc. The adhesive of the present invention is transparent when the adhesive is decomposed by a photoacid generator. The base sheet having may be suitably used.

  The thickness of the substrate sheet may be, for example, 1 to 300 μm (for example, 2 to 200 μm), preferably 3 to 100 μm, and more preferably about 5 to 80 μm. In addition, the substrate sheet may be formed by a conventional surface treatment such as oxidation treatment [surface oxidation treatment, eg, discharge treatment (corona discharge treatment, glow discharge, etc.), acid treatment (chromic acid treatment, etc.), ultraviolet irradiation treatment, soot Surface treatment such as treatment, etc., surface unevenness treatment (solvent treatment, sandblast treatment, etc.) may be applied.

  The laminated sheet can be obtained by a method of coating an adhesive on the base sheet, a method of laminating (adhering) the base sheet and the sheet-like adhesive, or the like.

  The adhesive of the present invention has adhesiveness (particularly hot melt adhesiveness) and has a property of being easily decomposed by an acid. Therefore, the adhesive of the present invention (particularly, an adhesive containing an acid generator) is useful as a temporary fixing adhesive. That is, such an adhesive adheres to the adherend, but the acid generated from the acid generator decreases the adhesive force with decomposition of the cyclic acetal compound (cyclic acetal structure), and can be easily peeled off ( Therefore, it can be used as a temporary fixing adhesive for temporarily fixing or temporarily bonding the adherend.

  Such temporary fixing adhesive is not particularly limited. For example, an adhesive (sheet-like) for protecting (or holding or fixing) an object to be polished (wafer or the like) during polishing (back grinding treatment). Adhesive). That is, such an adhesive can be used as an adhesive for a so-called back grind tape (back grind film) (or an adhesive constituting an adhesive layer of the back grind tape).

  The bonding method of the present invention includes a step (bonding step) of bonding the adherend using the adhesive. In particular, in a bonding method using an adhesive containing an acid generator (temporary bonding method), after the bonding step, an acid is further generated from the acid generator to decompose the adhesive (or cyclic acetal compound) ( Decomposition step). By passing through such a disassembling process, a non-bonded state can be easily formed after bonding, and temporary fixing becomes possible.

  Specifically, in the temporary fixing method (temporary bonding method) of the present invention, an adhesion step of adhering an adherend using the adhesive (adhesive containing an acid generator), and an adhering adherend Among them, a decomposition step of decomposing the adhesive (or cyclic acetal compound) with the acid generated from the acid generator by irradiating at least the adhesive interface (adhesive interface bonded with the adhesive) with active energy rays, and the bonded substrate A separation step of separating the adherend and the decomposed adhesive from the adherend (specifically, separating the adherend to make it non-adhered).

  In particular, such a temporary fixing method (temporary bonding method) can be applied to the back grinding treatment of a material to be polished (such as a wafer) as described above. Specifically, the processing method (polishing method, manufacturing method of polished polished material (wafer etc.)) of the material to be polished (wafer etc.) of the present invention is the adhesive (adhesive containing acid generator). And a wafer as an adherend (or by laminating the adhesive on a material to be polished (wafer or the like)) to obtain a laminate, and a material (wafer or the like) constituting the layered product ), The surface opposite to the adhesive surface is polished (back grind treatment), and at least the adhesive interface of the polished laminate is irradiated with active energy rays to generate an acid. A decomposition step of decomposing the adhesive with the acid generated from the generating agent, and a separation step of separating the polished material (wafer or the like) as the adherend from the laminated body and the decomposed adhesive.

  In the bonding step, the adherend and the adhesive are brought into contact with each other, but the contact method is not particularly limited. For example, (1) an adhesive containing a liquid adhesive or a solvent is applied to the adherend. A method of coating, (2) a method of coating (or spraying) a solid (powder) adhesive on the adherend, and (3) a method of laminating an adhesive formed into a sheet or the like on the adherend. Etc.

  When coating, the coating method is not particularly limited, and conventional methods such as a casting method, a spin coating method, a spray coating method, a bar coating method, a roll coating method, a gravure coating method, and a dipping method can be used.

  In the case of an adhesive containing a solvent, it may be dried as necessary after application. Drying may be performed under heating (for example, about 50 to 150 ° C., preferably about 60 to 130 ° C.) or under reduced pressure. In addition, by drying under heating, polymerization of a cyclic acetal compound having polymerizability can be advanced in the same manner as described later.

  In the bonding step, the thickness of the adhesive (adhesive layer) is, for example, 0.5 to 300 μm, preferably 1 to 200 μm, preferably 1.5 to 100 μm, and more preferably about 2 to 80 μm. Good.

  In the bonding step, in particular, an adhesive that is solid at normal temperature (an adhesive having a solid content or an adhesive component that is solid when a solvent is included) may be used and bonded by hot melt (thermal fusion). In such hot melt bonding, the heating temperature (hot melt bonding temperature) may be, for example, 50 to 170 ° C, preferably 80 to 160 ° C, and more preferably about 100 to 150 ° C. In the bonding step, an adherend [for example, a material to be polished (such as a wafer)] and an adhesive may be bonded (or laminated) under pressure as necessary. Moreover, at the time of such a heating, the polymeric cyclic acetal compound can also be superposed | polymerized simultaneously and the adhesive interface excellent in heat resistance and adhesiveness can be formed.

  In the back grinding process, the material to be polished (wafer or the like) is polished by polishing the surface opposite to the bonding surface while fixing the laminate. You may fix a laminated body using a suitable fixing means.

  The thickness of the polished material (wafer or the like) after polishing may be, for example, about 1 to 1000 μm, preferably 5 to 700 μm, and more preferably about 10 to 500 μm (for example, 30 to 400 μm).

  In the decomposition process, at least the adhesive interface is irradiated with active energy rays. The active energy ray may be either a heat ray or an actinic ray, or both. Usually, when the acid generator is a thermal acid generator, at least heat rays are applied (heated), and when the acid generator is a photoacid generator, at least active light is applied (irradiated).

  In the case of heating, the heating temperature may be, for example, 60 to 170 ° C, preferably 80 to 160 ° C, and more preferably about 100 to 150 ° C.

As the active light, radiation, ultraviolet light, visible light or the like can be used, and it may be usually ultraviolet light. As the light source, for example, in the case of ultraviolet rays, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a halogen lamp, a laser light source, or the like can be used. The irradiation amount (irradiation energy), for example, 10 to 10000 mJ / cm ^2, preferably 30~7000mJ / cm ^2, more preferably about 100~5000mJ / cm ^2. The irradiation time is not particularly limited, and may be, for example, about 5 seconds (for example, 10 seconds to 10 minutes), preferably about 15 seconds or more (for example, 20 seconds to 5 minutes).

  If necessary, heat treatment (after-cure or post-bake) may be performed after irradiation with actinic rays. The heating temperature may be, for example, about 80 to 180 ° C, preferably 100 to 170 ° C, and more preferably about 120 to 160 ° C. The heat treatment time may be, for example, about 3 seconds or more (for example, 5 seconds to 10 minutes), preferably about 5 seconds or more (for example, 7 seconds to 5 minutes).

  By undergoing such a decomposition step, the cyclic acetal compound is decomposed (liquefied), and the adhesive force by the adhesive is greatly reduced. Therefore, in the separation step, the adherend (polished wafer) and the decomposed adhesive are easily separated. Usually, the adhesive is separated by peeling off the adhesive from the adherend (the end of the adhesive layer is lifted in an oblique direction to the adherend and peeled off). Since the adhesiveness is extremely lowered after the decomposition, the adhesive can be easily separated without requiring such peeling. For example, these can be separated by simply sliding the adherend (wafer) with respect to the adhesive (or the substrate having the adhesive) (sliding the adherend along the adhesion interface). Therefore, as in the case of the separation (peeling) of the adhesive, after the back grinding treatment, when the adherend cannot require excessive strength (for example, the adherend may be torn), It is preferable to separate by sliding.

  The adhesive of the present invention is not particularly limited to temperature, and can be decomposed by acid over a wide range of temperatures. Therefore, the decomposition step can be performed in a wide temperature range (for example, normal temperature to 150 ° C.) regardless of whether the acid generator is a thermal acid generator.

  In this way, after the decomposition step, the adhesive can be easily separated, but when separated by a slide or the like, the decomposed adhesive (cyclic acetal compound) is deposited on the adherend (for example, an abrasive such as a wafer). May remain. Therefore, after the separation step, a cleaning step of cleaning an adhesive surface of the adherend (for example, an object to be polished such as a wafer) with the adhesive may be included. Cleaning may be performed simply by wiping off the adhesive surface, or may be cleaning with a solvent. Since the decomposition product of the cyclic acetal compound is dissolved in a general-purpose solvent (the same solvent as described above), like the cyclic acetal compound, the adhesive can be easily washed.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

GPC (gel permeation chromatography), NMR, viscosity, and thermal decomposition analysis were measured with the following equipment (and conditions).
GPC: Tosoh HLC-8220 column, Tosoh TSKgel SuperHZM-M × 3, polystyrene conversion NMR: JEOL ECA-500 Measuring method: Deuterated chloroform dilution viscosity: Rheometer (Physica MCR301), swing angle (γ ( gamma) = 5%), and measurement was performed while applying vibration of 10 Hz.
Thermal decomposition measurement (5% by weight reduction temperature): The sample was vacuum-dried at 100 ° C. for 1 hour, and then a temperature range of 25 to 550 ° C. and a temperature increase rate of 10 in a nitrogen atmosphere using TGDTA6300 manufactured by Seiko Instruments Inc. Simultaneous measurement of differential heat and thermogravimetry (TGDTA measurement) was performed under the conditions of ° C / min, and the temperature at which the weight decreased by 5% by weight was measured.

Example 1
To a flask in a nitrogen atmosphere, 4.1 g (31 mmol) of isophthalaldehyde, 3.9 g (31 mmol) of cyclohexyl vinyl ether and 34 mL of dehydrated tetrahydrofuran (THF) were added and cooled to −10 ° C. in an ice bath. While stirring, 5 cc of a toluene solution containing ethylaluminum dichloride at a concentration of 200 mM (that is, 1 mmol of ethylaluminum dichloride) was added with a syringe. Thereafter, when 2 hours passed while stirring at -10 to 0 ° C, 5 cc of a toluene solution containing ethylaluminum dichloride at a concentration of 200 mM (that is, 1 mmol of ethylaluminum dichloride) was further added by a syringe. When the reaction had elapsed for 5 hours, 0.8 g (8 mmol) of triethylamine was added, and then 1 g of water was added. When this liquid was analyzed, each conversion rate was 82% for isophthalaldehyde and 99% for cyclohexyl vinyl ether.

  This reaction solution was diluted with 300 mL of dichloromethane and washed with water by adding 300 mL of water. Then, it concentrated at 30 degreeC and 5 torr, and the weight after concentration was 8.7g. The concentrate was diluted with 20 g of ethyl acetate, dropped into 200 mL of n-hexane, and reprecipitation was performed. Decanted and dried to give 4.5 g of solid. When the molecular weight of the obtained solid was measured by GPC, the number average molecular weight (Mn) was 860, and the weight average molecular weight (Mw) was 1200. Further, it was confirmed by NMR measurement that the obtained solid was a polymer (multimer) having a structure (unit) represented by the following formula as a repeating unit.

¹ H-NMR (CDCl ₃ ): δ (ppm) = 9.9 to 10.1 (m), 7 to 8.1 (m), 5.6 to 5.8, 6.2 to 6.3 ( m), 4.3-5.5 (m), 3.6-3.8 (m), 2.2-2.5 (m), 0.9-2.1 (m).

  It was 230 degreeC when the 5 weight% reduction | decrease temperature of the obtained polymer was measured.

Using the obtained polymer, an adhesion test was performed as follows. That is, the obtained polymer was dissolved in ethyl acetate to prepare a 50% solution, and 5 parts by weight of an acid generator (triphenylsulfonium perfluoro-1-butanesulfonate) was mixed with 100 parts by weight of the polymer. Thus, a mixed resin solution was obtained. The mixed resin solution is applied on a silicon substrate by spin coating (1000 rpm) to a thickness of 3 μm and vacuum-dried at 100 ° C. for 1 hour to form a coating film (adhesive layer). Bonding was performed while applying pressure at 0 ° C. In addition, the adhesive layer became sticky by heating at 100 ° C., and exhibited hot-melt adhesiveness. Moreover, the size of the coating film (adhesion part) was 5 cm ² (20 mm × 25 mm). The viscosity of the obtained polymer at 100 ° C. was 0.1 Pa · s.

The adhesive strength of the adhesive layer was measured at room temperature as the minimum strength per unit area (tensile strength) when the quartz glass (and silicon) was pulled parallel to the adhesive surface (coating surface) and peeled off. However, it was 35 N / cm ² .

And after irradiating ultraviolet light (365 nm, 800 mJ, 40 seconds) using an ultraviolet light irradiation machine (USHIO Corporation, SPOT CURE UIS-25102, high-pressure mercury lamp) on the bonded portion and baking at 150 ° C. for 10 seconds When the tensile strength was measured in the same manner as described above, it was 6 N / cm ² , and the adhesive strength was remarkably reduced, so that it was easily peeled off (it can be peeled off simply by sliding the quartz glass parallel to the bonding surface). ) When the coating film forming part (adhesive residue) of the silicon substrate was washed with THF, the silicon substrate could be easily washed without remaining undissolved.

(Example 2)
In a nitrogen atmosphere flask, 5.2 g of diethylene glycol monovinyl monoacrylate containing 12.4 g (92 mmol) of isophthalaldehyde, 8.2 g (65 mmol) of cyclohexyl vinyl ether, and a radical polymerization inhibitor (CIBA: Irganox 1010) at a ratio of about 500 ppm ( 28 mmol), 100 mL of dehydrated THF was added, and the mixture was cooled to −10 ° C. in an ice bath. While stirring, 15 cc of a toluene solution containing ethylaluminum dichloride at a concentration of 200 mM (that is, 3 mmol of ethylaluminum dichloride) was added with a syringe. Thereafter, 15 cc (3 mmol) of a toluene solution containing ethylaluminum dichloride at a concentration of 200 mM was added with a syringe at the elapse of 1 hour and 2 hours with stirring at −10 to 0 ° C., respectively. When the reaction was over 4 hours, 2.4 g (24 mmol) of triethylamine was added, and then 5 g of water was added. When this liquid was analyzed, the respective conversion rates were 92% for isophthalaldehyde, 99% for cyclohexyl vinyl ether, and 78% for diethylene glycol monovinyl acrylate.

  The reaction solution was diluted with 1 L of dichloromethane, and water (500 mL) was added and washed with water. Then, it concentrated at 30 degreeC and 5 torr, and the weight after concentration was 28 g. The concentrate was diluted with 50 g of ethyl acetate, dropped into 1 L of n-hexane, and reprecipitation was performed. Decanted and dried to give 15 g of solid. When the molecular weight of the obtained solid was measured by GPC, Mn was 1060 and Mw was 2100. Moreover, it was confirmed by NMR measurement that the obtained solid was a polymer (multimer) having two structures (units) represented by the following formula as repeating units.

¹ H-NMR (CDCl ₃ ): δ (ppm) = 9.9 to 10.1 (m), 7 to 8.1 (m), 6.3 to 6.5 (m), 5.6 to 5 9.9, 6.2 to 6.3 (m), 6.0 to 6.2 (m), 4.3 to 5.5 (m), 3.6 to 4.1 (m), 2.2 -2.5 (m), 0.9-2.1 (m).

  It was 186 degreeC when the 5 weight% reduction | decrease temperature of the obtained polymer was measured.

  Using the obtained polymer, an adhesion test was conducted in the same manner as in Example 1. The mixed resin solution further proceeds with a polymerization (crosslinking) reaction with an acrylic group, so that 5 parts by weight of an acid generator, 3 parts by weight of a radical polymerization initiator (benzoyl peroxide) and radicals are added to 100 parts by weight of the polymer. A polymerization inhibitor (CIBA: Irganox 1010) to which 0.05 part by weight was added was used. The crosslinking reaction proceeded by heating at 100 ° C. Further, the viscosity of the obtained polymer at 100 ° C. was 3500 Pa · s.

Tensile strength before irradiation with ultraviolet light is tensile strength after baking at 49N / cm ^2, the ultraviolet light irradiation and 0.99 ° C. are 8N / cm ^2, the adhesive strength has been a significantly reduced to easily peeled off state (It was possible to remove it by simply sliding the quartz glass parallel to the bonding surface). In addition, when the coating film formation part (adhesive residue) of the silicon substrate was washed with ethyl acetate, the silicon substrate could be easily washed without remaining undissolved.

In addition, a coating film (adhesive layer) is formed on the silicon substrate by spin coating in the same manner as described above, and the adhesive layer and the quartz glass are arranged so that the quartz glass and the silicon substrate are perpendicular (cross). And laminated together while applying pressure at 100 ° C. The size of the coating film (adhesion part) was 4 cm ² (20 mm × 20 mm).

The adhesive strength of the adhesive layer is the minimum strength per unit area (surface peel strength) when quartz glass (and glass) is pulled perpendicular to the adhesive surface (coating surface) at 150 ° C and peeled off. It was 1.1 N / cm ² when measured.

And at 150 degreeC, when the surface peeling strength after irradiating an ultraviolet-ray (365nm, 800mJ, 40 second) to an adhesion part was measured similarly to the above, it was 0.1 N / cm < ² >, It was in a state where the force was remarkably lowered and it was easily peeled off (it could be peeled off simply by sliding the quartz glass parallel to the bonding surface). When the coating film forming part (adhesive residue) of the silicon substrate was washed with THF, the silicon substrate could be easily washed without remaining undissolved.

(Example 3)
In a nitrogen atmosphere flask, 2.9 g of diethylene glycol monovinyl monoacrylate containing 4.1 g (31 mmol) of isophthalaldehyde, 1.5 g (15 mmol) of isobutyl vinyl ether, and a radical polymerization inhibitor (CIBA: Irganox 1010) at a ratio of about 500 ppm ( 15 mmol), 34 mL of dehydrated THF was added, and the mixture was cooled to −10 ° C. in an ice bath. While stirring, 5 cc of a toluene solution containing ethylaluminum dichloride at a concentration of 200 mM (that is, 1 mmol of ethylaluminum dichloride) was added by a syringe. Thereafter, 5 cc (1 mmol) of a toluene solution containing ethylaluminum dichloride at a concentration of 200 mM was added with a syringe at the elapse of 1 hour and 2 hours with stirring at −10 to 0 ° C., respectively. When the reaction had elapsed for 5 hours, 0.8 g (8 mmol) of triethylamine was added, and then 5 g of water was added. When this liquid was analyzed, the respective conversion rates were 87% for isophthalaldehyde, 80% for isobutyl vinyl ether, and 83% for diethylene glycol monovinyl acrylate.

  This reaction solution was diluted with 300 mL of dichloromethane, and 300 mL of water was added and washed with water. Then, the weight after concentration concentrated at 30 ° C. and 5 torr was 8.6 g. The concentrate was diluted with 20 g of ethyl acetate, dropped into 200 mL of n-hexane, and reprecipitation was performed. Decanted and dried to give 5.8 g of solid. When the molecular weight of the obtained solid was measured by GPC, Mn was 1100 and Mw was 1880. Moreover, it was confirmed by NMR measurement that the obtained solid was a polymer (multimer) having two structures (units) represented by the following formula as repeating units.

¹ H-NMR (CDCl ₃ ): δ (ppm) = 9.9 to 10.1 (m), 7 to 8.1 (m), 5.6 to 5.8, 6.2 to 6.3 ( m), 4.3 to 5.5 (m), 3.6 to 3.8 (m), 3.2 to 3.4 (m), 2.1 to 2.5 (m), 0.8 -2.1 (m).

  It was 196 degreeC when the 5 weight% reduction | decrease temperature of the obtained polymer was measured.

  Using the obtained polymer, an adhesion test was conducted in the same manner as in Examples 1 and 2. The mixed resin solution further proceeds with a polymerization (crosslinking) reaction with an acrylic group, so that 5 parts by weight of an acid generator, 3 parts by weight of a radical polymerization initiator (benzoyl peroxide) and radicals are added to 100 parts by weight of the polymer. A polymerization inhibitor (CIBA: Irganox 1010) to which 0.05 part by weight was added was used. The crosslinking reaction proceeded by heating at 100 ° C. Further, the viscosity of the obtained polymer at 100 ° C. was 5000 Pa · s.

The tensile strength was measured at 0.99 ° C., a tensile strength before irradiation with ultraviolet light is 2.6 N / cm ^2, the tensile strength after baking with ultraviolet light irradiation and 0.99 ° C. is 0.4 N / cm ^2, The adhesive force was remarkably reduced, and it was easily peeled off with less force (the quartz glass could be peeled off simply by sliding it in parallel with the adhesive surface). In addition, when the coating film formation part (adhesive residue) of the silicon substrate was washed with ethyl acetate, the silicon substrate could be easily washed without remaining undissolved.

Further, the surface peel strength before irradiation with ultraviolet light is ^2.5 N / cm ² and the surface peel strength after irradiation with ultraviolet light is 0.4 N / cm ^2. It was in a state (it could be peeled off simply by sliding the quartz glass parallel to the bonding surface). In addition, when the coating film formation part (adhesive residue) of the silicon substrate was washed with ethyl acetate, the silicon substrate could be easily washed without remaining undissolved.

Example 4
1. Diethylene glycol monovinyl monoacrylate containing 4.1 g (31 mmol) of isophthalaldehyde, 1.5 g (15 mmol) of n-butyl vinyl ether and a radical polymerization inhibitor (manufactured by CIBA: Irganox 1010) in a nitrogen atmosphere flask at a ratio of about 500 ppm. 9 g (15 mmol) and 34 mL of dehydrated THF were added and cooled to −10 ° C. in an ice bath. While stirring, 5 cc of a toluene solution containing ethylaluminum dichloride at a concentration of 200 mM (that is, 1 mmol of ethylaluminum dichloride) was added by a syringe. Thereafter, 5 cc (1 mmol) of a toluene solution containing ethylaluminum dichloride at a concentration of 200 mM was added with a syringe at the elapse of 1 hour and 2 hours with stirring at −10 to 0 ° C., respectively. When the reaction had elapsed for 5 hours, 0.8 g (8 mmol) of triethylamine was added, and then 5 g of water was added. When this liquid was analyzed, the respective conversion rates were 80% for isophthalaldehyde, 70% for n-butyl vinyl ether, and 65% for diethylene glycol monovinyl acrylate.

  This reaction solution was diluted with 300 mL of dichloromethane, and 300 mL of water was added and washed with water. Then, it concentrated at 30 degreeC and 5 torr, and the weight after concentration was 5.7g. The concentrate was diluted with 20 g of ethyl acetate, dropped into 200 mL of n-hexane, and reprecipitation was performed. Decanted and dried to give 5.8 g of solid. When the molecular weight of the obtained solid was measured by GPC, Mn was 800 and Mw was 1100. Moreover, it was confirmed by NMR measurement that the obtained solid was a polymer (multimer) having two structures (units) represented by the following formula as repeating units.

¹ H-NMR (CDCl ₃ ): δ (ppm) = 9.9 to 10.1 (m), 7 to 8.1 (m), 5.6 to 5.8, 6.2 to 6.3 ( m), 4.3-5.5 (m), 3.3-3.8 (m), 2.2-2.5 (m), 0.7-2.1 (m).

  It was 208 degreeC when the 5 weight% reduction | decrease temperature of the obtained polymer was measured.

  Using the obtained polymer, an adhesion test was conducted in the same manner as in Examples 1 and 2. The mixed resin solution further proceeds with a polymerization (crosslinking) reaction with an acrylic group, so that 5 parts by weight of an acid generator, 3 parts by weight of a radical polymerization initiator (benzoyl peroxide) and radicals are added to 100 parts by weight of the polymer. A polymerization inhibitor (CIBA: Irganox 1010) to which 0.05 part by weight was added was used. The crosslinking reaction proceeded by heating at 100 ° C. Further, the viscosity of the obtained polymer at 100 ° C. was 4800 Pa · s.

When the tensile strength was measured at 150 ° C., the tensile strength before irradiation with ultraviolet light was 2.0 N / cm ² , and the tensile strength after baking with ultraviolet light irradiation and 150 ° C. was 0.1 N / cm ² , The adhesive force was remarkably reduced, and it was easily peeled off with less force (the quartz glass could be peeled off simply by sliding it in parallel with the adhesive surface). In addition, when the coating film formation part (adhesive residue) of the silicon substrate was washed with ethyl acetate, the silicon substrate could be easily washed without remaining undissolved.

Moreover, the surface peel strength before irradiation with ultraviolet light is 1.3 N / cm ² , and the surface peel strength after ultraviolet light irradiation is 0.1 N / cm ^2. It was in a state (it could be peeled off simply by sliding the quartz glass parallel to the bonding surface). In addition, when the coating film formation part (adhesive residue) of the silicon substrate was washed with ethyl acetate, the silicon substrate could be easily washed without remaining undissolved.

(Example 5)
In a nitrogen atmosphere flask, 3.5 g of diethylene glycol monovinyl monoacrylate containing 12.4 g (92 mmol) of isophthalaldehyde, 9.4 g (74 mmol) of cyclohexyl vinyl ether, and a radical polymerization inhibitor (CIBA: Irganox 1010) at a ratio of about 500 ppm ( 18 mmol), 100 mL of dehydrated THF was added, and the mixture was cooled to −10 ° C. in an ice bath. While stirring, 15 cc of a toluene solution containing ethylaluminum dichloride at a concentration of 200 mM (that is, 3 mmol of ethylaluminum dichloride) was added with a syringe. Thereafter, 15 cc (3 mmol) of a toluene solution containing ethylaluminum dichloride at a concentration of 200 mM was added with a syringe at the elapse of 1 hour and 2 hours with stirring at −10 to 0 ° C., respectively. When the reaction was over 4 hours, 2.4 g (24 mmol) of triethylamine was added, and then 5 g of water was added. When this liquid was analyzed, each conversion rate was 92% for isophthalaldehyde, 99% for cyclohexyl vinyl ether, and 80% for diethylene glycol monovinyl acrylate.

  The reaction solution was diluted with 1 L of dichloromethane, and water (500 mL) was added and washed with water. Then, it concentrated at 30 degreeC and 5 torr, and the weight after concentration was 28 g. The concentrate was diluted with 50 g of ethyl acetate, dropped into 1 L of n-hexane, and reprecipitation was performed. Decanted and dried to give 15 g of solid. When the molecular weight of the obtained solid was measured by GPC, Mn was 1000 and Mw was 1500. Moreover, it was confirmed by NMR measurement that the obtained solid was a polymer (multimer) having two structures (units) represented by the following formula as repeating units.

¹ H-NMR (CDCl ₃ ): δ (ppm) = 9.9 to 10.1 (m), 7 to 8.1 (m), 6.3 to 6.5 (m), 5.6 to 5 9.9, 6.2 to 6.3 (m), 6.0 to 6.2 (m), 4.3 to 5.5 (m), 3.6 to 4.1 (m), 2.2 -2.5 (m), 0.9-2.1 (m).

  It was 170 degreeC when the 5 weight% reduction | decrease temperature of the obtained polymer was measured.

  Using the obtained polymer, an adhesion test was conducted in the same manner as in Examples 1 and 2. The mixed resin solution further proceeds with a polymerization (crosslinking) reaction with an acrylic group, so that 5 parts by weight of an acid generator, 3 parts by weight of a radical polymerization initiator (benzoyl peroxide) and radicals are added to 100 parts by weight of the polymer. A polymerization inhibitor (CIBA: Irganox 1010) to which 0.05 part by weight was added was used. The crosslinking reaction proceeded by heating at 100 ° C. Further, the viscosity of the obtained polymer at 100 ° C. was 2 Pa · s.

Tensile strength before irradiation with ultraviolet light is tensile strength after baking at 28N / cm ^2, the ultraviolet light irradiation and 0.99 ° C. are 9N / cm ^2, the adhesive strength has been a significantly reduced to easily peeled off state (It was possible to remove it by simply sliding the quartz glass parallel to the bonding surface). In addition, when the coating film formation part (adhesive residue) of the silicon substrate was washed with ethyl acetate, the silicon substrate could be easily washed without remaining undissolved.

The surface peel strength before irradiation with ultraviolet light is 1.5 N / cm ^2, surface peel strength after ultraviolet light irradiation was 0.1 N / cm ^2, likewise, easily peeled off and significantly reduced adhesive strength It was in a state (it could be peeled off simply by sliding the quartz glass parallel to the bonding surface). In addition, when the coating film formation part (adhesive residue) of the silicon substrate was washed with ethyl acetate, the silicon substrate could be easily washed without remaining undissolved.

(Example 6)
In a nitrogen atmosphere flask, 8.6 g of diethylene glycol monovinyl monoacrylate containing 12.4 g (92 mmol) of isophthalaldehyde, 5.8 g (46 mmol) of cyclohexyl vinyl ether, and a radical polymerization inhibitor (CIBA: Irganox 1010) at a ratio of about 500 ppm ( 46 mmol), 100 mL of dehydrated THF was added, and the mixture was cooled to −10 ° C. in an ice bath. While stirring, 15 cc of a toluene solution containing ethylaluminum dichloride at a concentration of 200 mM (that is, 3 mmol of ethylaluminum dichloride) was added with a syringe. Thereafter, 15 cc (3 mmol) of a toluene solution containing ethylaluminum dichloride at a concentration of 200 mM was added with a syringe at the elapse of 1 hour and 2 hours with stirring at −10 to 0 ° C., respectively. When the reaction was over 4 hours, 2.4 g (24 mmol) of triethylamine was added, and then 5 g of water was added. When this liquid was analyzed, each conversion rate was 85% for isophthalaldehyde, 97% for cyclohexyl vinyl ether, and 85% for diethylene glycol monovinyl acrylate.

  The reaction solution was diluted with 1 L of dichloromethane, and water (500 mL) was added and washed with water. Then, it concentrated at 30 degreeC and 5 torr, and the weight after concentration was 28 g. The concentrate was diluted with 50 g of ethyl acetate, dropped into 1 L of n-hexane, and reprecipitation was performed. Decanted and dried to give 15 g of solid. When the molecular weight of the obtained solid was measured by GPC, Mn was 800 and Mw was 1100. Moreover, it was confirmed by NMR measurement that the obtained solid was a polymer (multimer) having two structures (units) represented by the following formula as repeating units.

¹ H-NMR (CDCl ₃ ): δ (ppm) = 9.9 to 10.1 (m), 7 to 8.1 (m), 6.3 to 6.5 (m), 5.6 to 5 9.9, 6.2 to 6.3 (m), 6.0 to 6.2 (m), 4.3 to 5.5 (m), 3.6 to 4.1 (m), 2.2 -2.5 (m), 0.9-2.1 (m).

  It was 206 degreeC when the 5 weight% reduction | decrease temperature of the obtained polymer was measured.

  Using the obtained polymer, an adhesion test was conducted in the same manner as in Examples 1 and 2. The mixed resin solution further proceeds with a polymerization (crosslinking) reaction with an acrylic group, so that 5 parts by weight of an acid generator, 3 parts by weight of a radical polymerization initiator (benzoyl peroxide) and radicals are added to 100 parts by weight of the polymer. A polymerization inhibitor (CIBA: Irganox 1010) to which 0.05 part by weight was added was used. The crosslinking reaction proceeded by heating at 100 ° C. Further, the viscosity of the obtained polymer at 100 ° C. was 5000 Pa · s.

Tensile strength before irradiation with ultraviolet light is 28N / cm ^2, the tensile strength after baking with ultraviolet light irradiation and 0.99 ° C. is 5N / cm ^2, the adhesive strength has been a significantly reduced to easily peeled off state (It was possible to remove it by simply sliding the quartz glass parallel to the bonding surface). In addition, when the coating film formation part (adhesive residue) of the silicon substrate was washed with ethyl acetate, the silicon substrate could be easily washed without remaining undissolved.

(Example 7)
To a flask in a nitrogen atmosphere, 4.1 g (31 mmol) of isophthalaldehyde, 2.2 g (31 mmol) of ethyl vinyl ether and 34 mL of dehydrated THF were added, and cooled to −10 ° C. in an ice bath. While stirring, 5 cc of a toluene solution containing ethylaluminum dichloride at a concentration of 200 mM (that is, 1 mmol of ethylaluminum dichloride) was added with a syringe. Thereafter, 5 cc of a toluene solution containing ethylaluminum dichloride at a concentration of 200 mM (that is, 1 mmol of ethylaluminum dichloride) was further added with a syringe at the time of 1 hour and 2 hours with stirring at -10 to 0 ° C. When the reaction was over 4 hours, 0.8 g (8 mmol) of triethylamine was added, and then 4 g of water was added. When this liquid was analyzed, the respective conversion rates were 93% for isophthalaldehyde and 83% for ethyl vinyl ether.

  The reaction solution was concentrated under reduced pressure of 10 Torr, diluted with 30 mL of ethyl acetate, and washed with water by adding 150 mL of water. Thereafter, the organic layer was concentrated at 30 ° C. and 5 torr, and the weight after concentration was 6.0 g. The concentrate was diluted with 15 g of ethyl acetate, dropped into 70 mL of n-hexane, and reprecipitation was performed. Decanted and dried to give 5.3 g of solid. When the molecular weight of the obtained solid was measured by GPC, the number average molecular weight (Mn) was 1200, and the weight average molecular weight (Mw) was 1,700. Further, it was confirmed by NMR measurement that the obtained solid was a polymer (multimer) having a structure (unit) represented by the following formula as a repeating unit.

¹ H-NMR (CDCl ₃ ): δ (ppm) = 9.9 to 10.1 (m), 7 to 8.1 (m), 6.2 to 6.4 (m), 5.7 to 5 .9 (m), 3.0 to 5.5 (m), 1.6 to 2.7 (m), 0.7 to 1.4 (m).

  It was 257 degreeC when the 5 weight% reduction | decrease temperature of the obtained polymer was measured.

  Further, an adhesion test was conducted in the same manner as in Example 1 using the obtained polymer. The viscosity of the obtained polymer at 100 ° C. was 1 Pa · s.

The tensile strength before irradiation with ultraviolet light was 28 N / cm ² , and after irradiation with ultraviolet light and baking at 150 ° C., the adhesive strength was remarkably reduced and the film was easily peeled off as in Example 1 (on the adhesive surface). It was possible to remove it by simply sliding the quartz glass in parallel. In addition, when the coating film formation part (adhesive residue) of the silicon substrate was washed with ethyl acetate, the silicon substrate could be easily washed without remaining undissolved.

(Example 8)
In a nitrogen atmosphere flask, 1.1 g of diethylene glycol monovinyl monoacrylate containing 4.1 g (31 mmol) of isophthalaldehyde, 1.8 g (25 mmol) of ethyl vinyl ether and a radical polymerization inhibitor (CIBA: Irganox 1010) at a ratio of about 500 ppm ( 6 mmol), 34 mL of dehydrated THF was added, and the mixture was cooled to −10 ° C. in an ice bath. While stirring, 5 cc of a toluene solution containing ethylaluminum dichloride at a concentration of 200 mM (that is, 1 mmol of ethylaluminum dichloride) was added by a syringe. Thereafter, 5 cc (1 mmol) of a toluene solution containing ethylaluminum dichloride at a concentration of 200 mM was added with a syringe at the elapse of 1 hour and 2 hours with stirring at −10 to 0 ° C., respectively. When the reaction was over 4 hours, 0.8 g (8 mmol) of triethylamine was added, and then 4 g of water was added. When this liquid was analyzed, the respective conversion rates were 90% for isophthalaldehyde, 83% for ethyl vinyl ether, and 78% for diethylene glycol monovinyl monoacrylate.

  The reaction solution was concentrated under reduced pressure of 10 Torr, diluted with 30 mL of ethyl acetate, and washed with water by adding 150 mL of water. Thereafter, the organic layer was concentrated at 30 ° C. and 5 torr, and the weight after concentration was 5.7 g. The concentrate was diluted with 15 g of ethyl acetate, dropped into 70 mL of n-hexane, and reprecipitation was performed. Decanted and dried to give 4.8 g of solid. When the molecular weight of the obtained solid was measured by GPC, the number average molecular weight (Mn) was 1300, and the weight average molecular weight (Mw) was 1800. Moreover, it was confirmed by NMR measurement that the obtained solid was a polymer (multimer) having two structures (units) represented by the following formula as repeating units.

¹ H-NMR (CDCl ₃ ): δ (ppm) = 9.9 to 10.1 (m), 7.1 to 8.2 (m), 6.1 to 6.5 (m), 5.7 -5.9 (m), 2.8-5.5 (m), 0.7-2.7 (m).

  It was 250 degreeC when the 5 weight% reduction | decrease temperature of the obtained polymer was measured.

  Further, an adhesion test was conducted in the same manner as in Example 1 using the obtained polymer. The resin solution further proceeds with a polymerization (crosslinking) reaction by an acrylic group, so that 5 parts by weight of an acid generator, 3 parts by weight of a radical polymerization initiator (benzoyl peroxide) and radical polymerization are performed with respect to 100 parts by weight of the polymer. What added 0.05 weight part of inhibitor (The product made from CIBA: Irganox1010) was used. The crosslinking reaction proceeded by heating at 100 ° C. Further, the viscosity of the obtained polymer at 100 ° C. was 3 Pa · s.

Further, the tensile strength before irradiation with ultraviolet light was 28 N / cm ² , and after the irradiation with ultraviolet light and baking at 150 ° C., the adhesive strength was remarkably reduced as in Example 1 (adhesion). It was possible to remove it simply by sliding the quartz glass parallel to the surface). In addition, when the coating film formation part (adhesive residue) of the silicon substrate was washed with ethyl acetate, the silicon substrate could be easily washed without remaining undissolved.

Example 9
1. Diethylene glycol monovinyl monoacrylate 1. Containing about 500 ppm of isophthalaldehyde 4.1 g (31 mmol), diethylene glycol monomethyl monovinyl ether 3.6 g (25 mmol), radical polymerization inhibitor (CIBA: Irganox 1010) in a nitrogen atmosphere flask. 1 g (6 mmol) and 34 mL of dehydrated THF were added, and the mixture was cooled to −10 ° C. in an ice bath. While stirring, 5 cc of a toluene solution containing ethylaluminum dichloride at a concentration of 200 mM (that is, 1 mmol of ethylaluminum dichloride) was added by a syringe. Thereafter, 5 cc (1 mmol) of a toluene solution containing ethylaluminum dichloride at a concentration of 200 mM was added with a syringe at the elapse of 1 hour and 2 hours with stirring at −10 to 0 ° C., respectively. When the reaction was over 4 hours, 0.8 g (8 mmol) of triethylamine was added, and then 4 g of water was added. When this liquid was analyzed, the respective conversion rates were 86% for isophthalaldehyde, 87% for diethylene glycol monomethyl monovinyl ether, and 80% for diethylene glycol monovinyl monoacrylate.

  The reaction solution was concentrated under reduced pressure of 10 Torr, diluted with 30 mL of ethyl acetate, and washed with water by adding 150 mL of water. Thereafter, the organic layer was concentrated at 30 ° C. and 5 torr, and the weight after concentration was 7.11 g. The concentrate was diluted with 15 g of ethyl acetate, dropped into 70 mL of n-hexane, and reprecipitation was performed. Decanted and dried to give 6.60 g of solid. When the molecular weight of the obtained solid was measured by GPC, the number average molecular weight (Mn) was 1200 and the weight average molecular weight (Mw) was 1970. Moreover, it was confirmed by NMR measurement that the obtained solid was a polymer (multimer) having two structures (units) represented by the following formula as repeating units.

¹ H-NMR (CDCl ₃ ): δ (ppm) = 9.9 to 10.1 (m), 7.2 to 8.6 (m), 6.3 to 6.5 (m), 6 to 6 0.2 (m), 5.7 to 5.8 (m), 3.2 to 5.5 (m), 1.1 to 2.7 (m).

  It was 185 degreeC when the 5 weight% reduction | decrease temperature of the obtained polymer was measured.

  Further, an adhesion test was conducted in the same manner as in Example 1 using the obtained polymer. The resin solution further proceeds with a polymerization (crosslinking) reaction by an acrylic group, so that 5 parts by weight of an acid generator, 3 parts by weight of a radical polymerization initiator (benzoyl peroxide) and radical polymerization are performed with respect to 100 parts by weight of the polymer. What added 0.05 weight part of inhibitor (The product made from CIBA: Irganox1010) was used. The crosslinking reaction proceeded by heating at 100 ° C. Further, the viscosity of the obtained polymer at 100 ° C. was 14.3 Pa · s.

Further, the tensile strength before irradiation with ultraviolet light was 12.70 N / cm ² , and after the irradiation with ultraviolet light and baking at 150 ° C., the adhesive strength was remarkably lowered and it was in a state of being easily peeled off as in Example 1. (It was possible to remove it by simply sliding the quartz glass parallel to the bonding surface). In addition, when the coating film formation part (adhesive residue) of the silicon substrate was washed with ethyl acetate, the silicon substrate could be easily washed without remaining undissolved.

(Example 10)
Diethylene glycol monovinyl monosilane containing 138 g of a toluene solution containing 3.1 g (31 mmol) of glutaraldehyde, 3.1 g (25 mmol) of cyclohexyl vinyl ether and a radical polymerization inhibitor (manufactured by CIBA: Irganox 1010) in a nitrogen atmosphere flask. 1.1 g (6 mmol) of acrylate was added and cooled to −10 ° C. in an ice bath. While stirring, 5 cc of a toluene solution containing ethylaluminum dichloride at a concentration of 200 mM (that is, 1 mmol of ethylaluminum dichloride) was added by a syringe. Thereafter, 5 cc (1 mmol) of a toluene solution containing ethylaluminum dichloride at a concentration of 200 mM was added with a syringe at the elapse of 1 hour and 2 hours with stirring at −10 to 0 ° C., respectively. When the reaction was over 4 hours, 0.8 g (8 mmol) of triethylamine was added, and then 4 g of water was added. When this liquid was analyzed, the respective conversion rates were 90% for isophthalaldehyde, 86% for cyclohexyl vinyl ether, and 80% for diethylene glycol monovinyl monoacrylate.

  The reaction solution was concentrated under reduced pressure of 10 Torr, diluted with 30 mL of ethyl acetate, and washed with water by adding 150 mL of water. Thereafter, the organic layer was concentrated at 30 ° C. and 5 torr, and the weight after concentration was 6 g. The concentrate was diluted with 15 g of ethyl acetate, dropped into 70 mL of n-hexane, and reprecipitation was performed. Decanted and dried to give 4.8 g of solid. When the molecular weight of the obtained solid was measured by GPC, the number average molecular weight (Mn) was 1400, and the weight average molecular weight (Mw) was 1800. Moreover, it was confirmed by NMR measurement that the obtained solid was a polymer (multimer) having two structures (units) represented by the following formula as repeating units.

¹ H-NMR (CDCl ₃ ): δ (ppm) = 9.7 to 9.8 (m), 6.4 to 6.5 (m), 6.1 to 6.3 (m), 4.4 -5.5 (m), 3.2-4.3 (m), 0.8-2.7 (m).

  It was 170 degreeC when the 5 weight% reduction | decrease temperature of the obtained polymer was measured.

  Further, an adhesion test was conducted in the same manner as in Example 1 using the obtained polymer. The resin solution further proceeds with a polymerization (crosslinking) reaction by an acrylic group, so that 5 parts by weight of an acid generator, 3 parts by weight of a radical polymerization initiator (benzoyl peroxide) and radical polymerization are performed with respect to 100 parts by weight of the polymer. What added 0.05 weight part of inhibitor (The product made from CIBA: Irganox1010) was used. The crosslinking reaction proceeded by heating at 100 ° C. Further, the viscosity of the obtained polymer at 100 ° C. was 1 Pa · s.

Further, the tensile strength before irradiation with ultraviolet light was 30 N / cm ² , and after the irradiation with ultraviolet light and baking at 150 ° C., the adhesive strength was remarkably lowered as in Example 1, and the film was easily peeled off (adhesion) It was possible to remove it simply by sliding the quartz glass parallel to the surface). In addition, when the coating film formation part (adhesive residue) of the silicon substrate was washed with ethyl acetate, the silicon substrate could be easily washed without remaining undissolved.

  The adhesive of the present invention has excellent adhesiveness and can achieve both adhesiveness and excellent decomposability by acid. Therefore, it is suitable as an adhesive for temporary fixing. In particular, the adhesive of the present invention is useful as an application that requires ease of peeling after bonding, for example, an adhesive in back grinding.

Claims (21)

Following formula (1)

Wherein R ¹ is a residue of a carbonyl compound, R ^2a and R ^2b are the same or different and are a hydrogen atom or a substituent, R ^{3 to} R ⁵ are the same or different and are a hydrogen atom or a substituent, and R ⁶ is a substituent. R ³ or R ⁴ and R ⁶ may be bonded to each other to form a ring.)
An adhesive comprising a cyclic acetal compound having a unit represented by: The adhesive according to claim 1, wherein R ¹ is a residue of a polycarbonyl compound, and the cyclic acetal compound is a multimeric compound having a unit represented by formula (1) as a repeating unit. The adhesive according to claim 2, wherein R ¹ is a direct bond or a divalent hydrocarbon group. The adhesive according to any one of claims 1 to ³ , wherein R ^2a and R ^2b are hydrogen atoms, and R ^{3 to} R ⁵ are hydrogen atoms or hydrocarbon groups. The unit according to any one of claims 1 to 4, which has at least one unit selected from a unit (1a) in which R ⁶ is a non-polymerizable substituent and a unit (1b) in which R ⁶ is a polymerizable substituent. adhesive.   The adhesive according to claim 5, wherein the non-polymerizable substituent is a saturated aliphatic hydrocarbon group, and the polymerizable substituent is an unsaturated aliphatic hydrocarbon group or a hydrocarbon group having a polymerizable group. R ¹ is a direct bond, an alkylene group or an arylene group, R ^2a and R ^2b are hydrogen atoms, R ^{3 to} R ⁵ are the same or different and are a hydrogen atom or an alkyl group, and the non-polymerizable substituent is an alkyl group The adhesive according to claim 5 or 6, which is a group, an alkoxyalkyl group, an alkoxy (poly) alkoxyalkyl group or a cycloalkyl group, and the polymerizable substituent is an alkenyl group or an alkyl group having a (meth) acryloyloxy group. . The adhesive according to claim 1, wherein R ¹ is a 1,2-phenylene group or a 1,3-phenylene group. The adhesive according to any one of claims 1 to 8, wherein R ⁶ has at least a unit (1b) in which R ⁶ is a polymerizable substituent. A unit (1a) R ⁶ is a non-polymerizable substituents, adhesive according to claim 1 and a unit (1b) R ⁶ is a polymerizable substituent.   The adhesive according to claim 10, wherein a ratio (molar ratio) between the unit (1a) and the unit (1b) is the former / the latter = 99/1 to 40/60.   The adhesive according to any one of claims 1 to 11, wherein the cyclic acetal compound has a weight average molecular weight of 800 or more.   The adhesive according to any one of claims 1 to 12, wherein the cyclic acetal compound has a 5% by weight reduction temperature of 150 ° C or higher.   The adhesive according to any one of claims 1 to 13, wherein the cyclic acetal compound is solid at normal temperature and has hot-melt adhesiveness.   Furthermore, it is the adhesive agent for temporary fixing containing an acid generator, The adhesive agent in any one of Claims 1-14.   An adhesion step of adhering an adherend using the adhesive according to claim 15, and an adhesive generated by an acid generated from an acid generator by irradiating at least an adhesion interface with active energy rays among the adhered adherend A method for temporarily adhering an adherend comprising: a disassembling step for disassembling the substrate; and a separating step for separating the adherend and the decomposed adhesive from the adherend to be adhered.   An adhesion step of bonding the adhesive according to claim 15 and a material to be polished as an adherend to obtain a laminate, and polishing a surface opposite to the adhesive surface among the materials to be polished constituting the laminate. A polishing step, a decomposition step of decomposing the adhesive with an acid generated from the acid generator by irradiating at least the bonding interface with an active energy ray, and polishing from the laminate as an adherend A method for processing a material to be polished comprising a separation step of separating the material to be polished and the decomposed adhesive.   The method according to claim 16 or 17, wherein, in the bonding step, a solid adhesive is used at normal temperature and is bonded by hot melt.   The method according to any one of claims 16 to 18, wherein, in the bonding step, the adhesive and the adherend are brought into contact with each other at 50 to 150 ° C to be bonded.   The method according to any one of claims 16 to 19, wherein in the separation step, the adherend is separated by sliding with respect to the adhesive.   The method according to any one of claims 16 to 20, further comprising, after the separation step, a washing step of washing an adhesive surface of the adherend with the adhesive.