CN105358602B

CN105358602B - Modified resin and resin combination

Info

Publication number: CN105358602B
Application number: CN201480038533.7A
Authority: CN
Inventors: 篠畑雅亮; 小杉裕士; 三宅信寿
Original assignee: Asahi Kasei Corp
Current assignee: Asahi Kasei Corp
Priority date: 2013-07-08
Filing date: 2014-07-07
Publication date: 2018-12-04
Anticipated expiration: 2034-07-07
Also published as: TWI570144B; TW201605915A; TW201605917A; CN113929866B; JPWO2015005283A1; KR101875294B1; TWI565725B; KR20160018726A; CN113929866A; CN107629183B; WO2015005283A1; TW201605916A; TW201522403A; CN107629183A; TWI564316B; CN105358602A; CN111205424A; TW201605918A; TWI543995B; TWI577705B

Abstract

The invention discloses a kind of with nitrogen-carbon-sulfide linkage resin.Nitrogen-carbon-sulfide linkage is made of nitrogen-atoms, carbon atom and sulphur atom, these atoms are bonded with the sequence, being bonded for carbon atom and sulphur atom and at least one of being bonded as singly bound for carbon atom and nitrogen-atoms.When composition nitrogen-carbon-sulfide linkage sulphur atom quantity that the number-average molecular weight of the resin is Mn, includes in every 1 molecule resin is n¹When, Mn is 500 or more, Mn/n¹It is 50 or more 300 or less.

Description

Modified resin and resin combination

Technical field

The present invention relates to modified resin and resin combinations.

Background technique

Isocyanates is known as the raw material of polyurethane and polyureas.

Polyurethane is to be manufactured by isocyanate group with reacting for hydroxyl, and tension stress, abrasion performance, oil resistivity are excellent It is different, it is used in coating, cement, automobile component etc..For example, Patent Document 1 discloses a kind of double groups for packaging film Divide polyurethane coating.

Polyureas is to be manufactured by isocyanate group with reacting for amino, heat resistance, mechanical strength, chemical-resistant resistance Property is excellent, is used in injection-molded article, film, fiber etc..For example, Patent Document 2 discloses a kind of engagements using polyureas Agent.

In this way, the polyurethane and polyureas of the reaction based on isocyanate group as coating or cement be coated to metal, The surface of glass, plastics, assigning function to its surface still thus must be abundant with the adaptation on surface.

As the method for improving adaptation, For example, Patent Document 3 discloses a kind of organic overlay films by surface of steel plate Handle the method to control the adaptation of carbamate.In addition, the ameliorative way as the resin side being coated with, for example, specially Disclose a kind of composition comprising polymer in sharp document 4, the polymer contain acid modified polyolefin system resin dispersion and Element sulphur.

Polyisocyantates composition comprising polyfunctional isocyanate compound (polyisocyanates) is used for Coating material composition The extensive purposes such as object.Such polyisocyantates composition for example goes out as one-pack-type or dual liquid type polyurethane coating composition It sells.Wherein, dual liquid type polyurethane coating composition is capable of forming fine and close crosslinking film, and finished appearance is good, thus The appearance and excellent weatherability, the purposes of durability of high-quality are required as the top coat layer use of automobile, information household appliances etc. In spoken highly of.

In the top coating of mobile applications, information household appliances purposes etc., other than appearance of high-quality etc., it is also desirable to have Marresistance and high rigidity.In addition, for the coating composition for being used to form top coating, it is desirable to have good stretch Malleability.

As the composition comprising polyisocyanates, such as propose: containing isocyanurate group and phosphorus concentration be 0.1~ The polyisocyantates composition (patent document 5) of 20ppm；Coating material composition containing the polyisocyanates with allophanate group Object (patent document 6, patent document 7)；Coating containing polyisocyantates composition and polyalcohol with allophanate group Composition (patent document 8) etc., manufacturing method to above-mentioned composition and using being studied.

The balancing good of heat resistance, the chemical resistance of epoxy resin etc., thus for example as coating, cement, at The materials such as profile material, composite material, laminated board, sealing material and be used in extensive field.

In recent years, compared with existing resin material, it is desirable that the resin material with significantly high performance, high reliability. Just existing resin is modified in the various modified gimmicks of research and utilization.Wherein, have make a part of oxide-base with it is different The modified epoxy of 1- oxa- -3- azacycloparaffin -2- ketone structure obtained from the reaction of cyanic acid ester group is high as that can take into account Glass transition temperature and flexible resin and attract attention, propose many schemes (referring for example to patent document 9, patent text Offer 10, patent document 11).

Existing technical literature

Patent document

Patent document 1: Japanese Unexamined Patent Application Publication 2012-517489 bulletin

Patent document 2: Japanese Unexamined Patent Application Publication 2010-507689 bulletin

Patent document 3: Japanese Unexamined Patent Publication 2001-219498 bulletin

Patent document 4: Japanese Unexamined Patent Publication 2010-163579 bulletin

Patent document 5: No. 4201582 bulletins of Japanese Patent No.

Patent document 6: Japanese Unexamined Patent Publication 8-188566 bulletin

Patent document 7: Japanese Unexamined Patent Publication 7-304724 bulletin

Patent document 8: International Publication No. 2002/32979

Patent document 9: Japanese Unexamined Patent Application 59-135265 bulletin

Patent document 10: Japanese Unexamined Patent Application 61-181820 bulletin

Patent document 11: Japanese Unexamined Patent Publication 5-222160 bulletin

Summary of the invention

Problems to be solved by the invention

The polyurethane and polyureas of reaction based on isocyanate group as coating or cement be coated to metal, glass, The surface of plastics assigns function to its surface, but requires the further improvement of heat resistance.

Therefore, from one aspect, the purpose of the present invention is to provide a kind of resin combinations of modification that heat resistance is high Object.

On the other hand, the method being surface-treated as described in Patent Document 3 is in many cases because of surface shape and table Plane materiel matter and be difficult to be applicable in.In addition, in the case where the resin compound as patent document 4, sometimes because resin is mutual Mutually separation and make adaptation instead and reduce or the function of film itself is impaired.

Therefore, from other side, the purpose of the present invention is to provide a kind of resin groups of modification that adaptation is high Close object.

In addition, according to the present invention people research it is found that the polyisocyantates composition recorded in patent document 5~8 with The aspect of the adaptation of adherend, particularly with the adaptation of metal in terms of there are rooms for improvement.

Further from other side, it is good with the adaptation of adherend that the purpose of the present invention is to provide a kind of Polyisothiocyanates and its manufacturing method.

In addition, the research of people is it is found that records in patent document 9~11 has 1- oxa- -3- azacyclo- according to the present invention The modified epoxy of alkane -2- ketone structure because its purposes difference, with the adaptation of adherend, particularly with metal There are rooms for improvement in terms of adaptation.

Further from other side, the issue of the present invention is to provide one kind to keep epoxy resin, epithio While the characteristic of the compounds such as resin and the good modified epoxy of the adaptation of adherend；It is closely sealed with adherend The compounds such as the good modified episulfide resin of property；And the manufacturing method of these compounds.

Solution for solving the problem

The present inventor has made intensive studies in order to solve the above problems, as a result, it has been found that, by having specific knot in molecule The resin of structure, containing make the compound with particular functional group react obtained from the resin of compound be able to solve above-mentioned class Topic, has thus completed the present invention.

That is, the present invention relates to following technical proposals.

[1]

A kind of resin, for nitrogen-carbon-sulfide linkage resin, the nitrogen-carbon-sulfide linkage is by nitrogen-atoms, carbon atom and sulphur atom Constitute, these atoms are bonded with the sequence, above-mentioned carbon atom and above-mentioned sulphur atom be bonded and above-mentioned carbon atom and above-mentioned nitrogen original At least one of bonding of son is singly bound, when the number-average molecular weight of the resin is Mn, includes in every 1 molecule resin Constituting above-mentioned nitrogen-carbon-sulfide linkage sulphur atom quantity is n₁When, Mn is 500 or more, Mn/n₁For 50 or more 300 hereinafter, n₁By Formula: n₁=X¹·Mn(X¹Indicate the quantity of the above-mentioned nitrogen-carbon-sulfide linkage sulphur atom of composition for including in every 1g resin) it calculates.

[2]

Resin as described in [1], wherein 5% thermal weight loss temperature of the resin is 300 DEG C or more.

[3]

A kind of resin, be by compound with following functional groups with selected from by monoisocyanates, polyisocyanates, Obtained from the reaction of at least one kind of compound in the group of monoisothiocyanates and polyisothiocyanates composition, which is At least one kind of functional group in the group being made of 1 valence group represented by following formula (1), (2), (3), (4) or (5).

-OH (I)-NH₂ (2)

[4]

Resin as described in [3] is by the above compound with following functional groups and selected from by single isothiocyanic acid The reaction of at least one kind of compound or monoisothiocyanates or polyisothiocyanates in ester and polyisothiocyanates and obtain Resin, the functional group be select 1 valence group represented by free style (1)~(5) form group at least one kind of functional group.

[5]

Resin as described in [3] or [4], wherein above-mentioned monoisothiocyanates includes chemical combination represented by following formula (30) Object or be the compound.

R⁵-NCS (30)

(in formula, R⁵Indicate organic group.R⁵Can be carbon atom number be 1~25 aliphatic group, with aromatic series The aromatic group that the aliphatic group or carbon atom number that the carbon atom number for closing object substitution is 7~25 are 6~25.)

[6]

Resin as described in any one of [3]~[5], wherein above-mentioned resin, which has, to be come from represented by formula (3)~(5) The cyclic structure of above-mentioned functional group and isocyanate group or isothiocyanate group reacted.

[7]

Resin as described in [6], wherein as the group for containing above-mentioned cyclic structure, there are 2 or more to be selected from by following At least one kind of structural unit (group) in the group of the composition of divalent group represented by formula (6), (7) or (8).

(in formula, Y¹Indicate organic group, 2 or more Y in same molecule¹It can be the same or different.Y¹It can be with For-NH- base.)

[8]

A kind of resin, the group that the divalent group represented by being selected from 2 or more by following formula (6), (7) or (8) forms In at least one kind of structural unit (group).

[9]

Resin as described in [7] or [8], wherein when the number-average molecular weight of the resin is Mn, is wrapped in every 1 molecule resin The sum of quantity of above structure unit represented by the formula (6), (7) or (8) contained is n₂When, Mn is 500 or more, Mn/n₂For 50 with Upper 300 hereinafter, n₂By formula: n₂=X₂·Mn(X₂Indicate above-mentioned represented by the formula (6), (7) or (8) for including in every 1g resin The sum of quantity of structural unit) it calculates.

[10]

A kind of resin, be as obtained from reacting with nitrogen-carbon-sulfide linkage compound and polyisothiocyanates, Nitrogen-carbon-the sulfide linkage is made of nitrogen-atoms, carbon atom and sulphur atom, these atoms are bonded with the sequence.

[11]

Resin as described in [3]~any one of [7] and [10], wherein above-mentioned polyisothiocyanates includes following formula (32) compound represented by or be the compound.

(in formula, R⁶Indicate that organic group, a indicate 2~1000 integer.)

[12]

Resin as described in [3]~any one of [7] and [10], wherein above-mentioned polyisothiocyanates include have 2 with The polymer of repetitive unit represented by upper following formula (33) or be the polymer.

(in formula, R⁷Indicate organic group,

R⁸Indicate organic group or singly-bound,

B indicates 1 or more integer,

G indicates 1 or 2,

2 or more R in same molecule⁷、R⁸, b and g can be the same or different respectively.)

[13]

Resin as described in [3]~any one of [7] and [10], wherein above-mentioned polyisothiocyanates includes following chemical combination Object or be the compound, which includes structural unit represented by 2 or more following formula (40)；With selected under State the group of 1 valence represented by formula (41), (42), (43), (44), (45), (46) or (47), divalent or trivalent group (unit) composition In at least one kind of structural unit, nitrogen-atoms and carbon atom bonding in the compound.

SCN-R³- (40)

(in formula, R³Indicate organic group, R⁴Indicate aliphatic group or aromatic group or aliphatic alkyl or fragrance Race's alkyl, X³Indicate oxygen atom or sulphur atom, 2 or more R in same molecule³、R⁴And X³It respectively can be identical or not Together.)

[14]

Resin as described in [3]~any one of [7] and [10], wherein above-mentioned polyisothiocyanates includes following formula (33) compound represented by or be the compound.

SCN-R³-NCS (33)

(in formula, R³Indicate organic group.)

[15]

A kind of resin, be by include the steps that by compound represented by following formula (33) polymerize method and obtain 's.

SCN-R³-NCS (33)

(in formula, R³Indicate organic group.)

[16]

[15] manufacturing method of the resin described in comprising following steps: in the presence of a catalyst by formula (33) institute table The above compound polymerization shown.

[17]

A kind of resin, includes

Structural unit represented by 2 or more following formula (40)；With

Selected from by 1 valence, divalent or the trivalent base represented by following formula (41), (42), (43), (44), (45), (46) or (47) At least one kind of structural unit in the group of group's (structural unit) composition,

Nitrogen-atoms (N) in 1 above structure unit represented by formula (41)~(47) not with formula (41)~(47) institute table Nitrogen-atoms (N) Direct Bonding in the other above structure units shown.

R in above structure unit represented by formula (41)~(47)³Can with isothiocyanate group Direct Bonding and shape The above structure unit of an accepted way of doing sth (40).

SCN-R³- (40)

(in formula, R³Indicate organic group, R⁴Indicate aliphatic group or aromatic group,

X³Indicate oxygen atom or sulphur atom,

2 or more R in same molecule³、R⁴And X³It can be the same or different respectively.)

[18]

Resin as described in [13], [14], [15] or [17], wherein R³For aliphatic group or aromatic group.

[19]

Resin as described in [18], wherein R³For following formula (301), (302), (303), (304), (305) or (306) Represented alkyl.

(in formula, i indicates 1~12 integer, can be 1~10.)

[20]

A kind of resin combination, it includes the resins described in any one of [1]~[15] and [17]~[19].

[21]

A kind of class coating material, the resin combination as described in [20] are formed or are formed using the resin combination.

[22]

A kind of aqueous coating contains resin combination described in [20].

[23]

A kind of resin, it includes strands represented by following formula (10).

(in formula, P¹Indicate aliphatic group and/or aromatic group, Q¹It indicates selected from by following formula (11), (12), (13) Or the structural unit (group) of one or more of group of the composition of divalent group represented by (14), 2 or more P¹And Q¹It can phase With can also be different, n indicates 2 or more integer.)

(in formula, R¹Indicate aliphatic group or aromatic group,

X²And Y²Separately indicate oxygen atom or sulphur atom, 2 or more R in same molecule¹、X²And Y²Difference can It can also be different with identical.One Q¹In X²And Y²In 1 the above are sulphur atoms.)

[24]

Resin as described in [23], wherein R¹It is that 2 isocyanides for constituting the polyisocyanates are removed from polyisocyanates Residue after perester radical (- NCO) or be that 2 different sulphur cyanogen for constituting the polyisothiocyanates are removed from polyisothiocyanates Residue after perester radical (- NCS).

[25]

Resin as described in [23] or [24] is by least 1 in polyisocyanates and polyisothiocyanates Obtained from the reacting of kind of compound and compound represented by following formula (20).

(in formula, R²Indicate aliphatic group or aromatic group,

Y²Indicate oxygen atom or sulphur atom.2 or more Y in one unit²It can be the same or different.)

[26]

Resin as described in [25], wherein at least one kind of above-mentioned chemical combination in polyisocyanates and polyisothiocyanates Object includes compound represented by following formula (31).

XCN-R¹-NCX (31)

(in formula, R¹Indicate aliphatic group or aromatic group,

X indicates oxygen atom or sulphur atom.X and Y in one unit²At least one of can be sulphur atom.)

[27]

Resin as described in [25] or [26], wherein R²It is represented for following formula (201), (202), (203) or (204) 1 valence group.

[28]

Resin as described in any one of [23]~[27], wherein R¹Be carbon atom number be 1~25 aliphatic group, The aliphatic group or carbon atom number that the carbon atom number replaced with aromatic group (aromatic compound) is 7~25 be 6~ 25 aromatic group.

[29]

Resin as described in any one of [23]~[27], wherein R¹Be selected from by following formula (301), (302), (303), the alkyl in the group of the composition of alkyl represented by (304), (305) or (306).

(in formula, i indicates 1~12 integer, can be 1~10.)

[30]

Resin as described in any one of [23]~[28], wherein R¹Without containing spiro-atom.

[31]

A kind of solidification compound, it includes the resins and curing agent described in any one of [23]~[30].

[32]

[25] or the manufacturing method of resin described in [26] comprising following steps: in the presence of a catalyst, make to be selected from At least one kind of above compound in polyisocyanates and polyisothiocyanates is reacted with above compound represented by formula (20).

The effect of invention

According to the present invention it is possible to provide a kind of resin combination of modification that heat resistance is high.

According to the present invention it is possible to provide a kind of resin combination of modification that adaptation is high.

According to the present invention it is possible to provide a kind of and the good polyisothiocyanates of adherend adaptation and its manufacturer Method.

According to the present invention it is possible to provide it is a kind of while keeping the characteristic of epoxy resin, the compounds such as episulfide resin with The good modified epoxy of the adaptation of adherend；With the chemical combination such as the good modified episulfide resin of the adaptation of adherend Object；And the manufacturing method of these compounds.

Detailed description of the invention

Fig. 1 is solid obtained in embodiment 17¹H-NMR spectrum.

Fig. 2 shows polyisothiocyanates¹The figure of H-NMR spectrum.

Fig. 3 is to show the compound comprising oxazolidine -2- thioketones ring¹The figure of H-NMR spectrum.

Specific embodiment

In the following, present embodiment (hereinafter referred to " present embodiment ") is described in detail.The present invention is unlimited In the following embodiments and the accompanying drawings, various modifications can be carried out in the range of its main points to implement.

In this specification, chemical combination name (is purely combined with applied chemistry the world using based on IUPAC in many cases Meeting) defined nomenclature (IUPAC organic chemistry nomenclature) in record rule title." organic " refers to as the rule Disclosed in nomenclature object universal compound group.The object can be the object recorded in the suggestion that 1993 propose. It wherein, also include organo-metallic compound and metal complex as " organic " compound of the object of above-mentioned nomenclature.This reality It applies in mode, uses " organic " and/or the terms such as " organic group " and/or " substituent group ", make in present embodiment as described below Compound, in the absence of special instructions, they are not by including metallic atom and/or semimetallic atomic building.? In present embodiment, as by being selected from H (hydrogen atom), C (carbon atom), N (nitrogen-atoms), O (oxygen atom), S (sulphur atom), Cl The structure of (chlorine atom), Br (bromine atom), atomic building in I (iodine atom), use " organic compound ", " organic group ", " substituent group ".

Use term as " aliphatic " and " aromatic series " in the following description more.According to the rule of above-mentioned IUPAC, It describes organic compound and is classified as aliphatic compound and aromatic compound.Aliphatic compound refers to according to being based on The definition of the group for the aliphatic compound that the IUPAC of nineteen ninety-five suggests.Aliphatic compound is defined as in the suggestion “Acyclic or cyclic,saturated or unsaturated carbon compounds,excluding Aromatic compounds (non-ring type or ring type, saturated or unsaturated carbon compound remove aromatic compound) ".In addition, The aliphatic compound and aliphatic group used in description of the present embodiment contains in saturation and unsaturated, chain and ring-type It is any, can by be selected from above-mentioned H (hydrogen atom)；C (carbon atom)；N (nitrogen-atoms)；O (oxygen atom)；S (sulphur atom)；Si (silicon atom)；Halogen atom in Cl (chlorine atom), Br (bromine atom) and I (iodine atom)；In atomic building.

As " aralkyl " there is the group for the aromatic group being bonded with aliphatic group be denoted as sometimes " with fragrance The aliphatic group that race's group replaces ", " aromatic-aliphatic group " " have been bonded the aliphatic group composition of aromatic group Group ".This is based on the reactivity in present embodiment, because of property relevant to the reaction of group as aralkyl extremely class It is similar to aliphatic reactivity, rather than armaticity.Also, the non-aromatic for containing aralkyl, alkyl etc. is reacted sometimes Property group be denoted as " can with aromatic series replace aliphatic group ", " with aromatic series replace aliphatic group ", " bonding Aliphatic group of aromatic group " etc., is included in sometimes in " aliphatic group ".

When illustrating the general formula of compound used in this specification, using according to rules of nomenclature as defined in above-mentioned IUPAC Definition then, still, the title of specific group, the compound name of illustration use trivial name sometimes.Also, this specification In, number, the number of substituent group, number of atom are recorded sometimes, they indicate integer.

In the case that substituent group, the compound illustrated in this specification has constitutional isomer, as long as not special declaration, Including their constitutional isomer.

Resin combination involved in several embodiments contains with nitrogen-carbon-sulfide linkage, and/or nitrogen-carbon-oxygen bond tree Rouge.Nitrogen-carbon-sulfide linkage described herein refer to nitrogen-atoms, carbon atom, sulphur atom with the sequence bonding and the structure of state, the key In nitrogen-bond with carbon, the conjunction of carbon-sulfide linkage can be singly bound, or unsaturated bond is bonded.Wherein, nitrogen-bond with carbon and At least one of carbon-sulfide linkage conjunction can be singly bound.The nitrogen-atoms and sulphur atom for forming the key can be by other atoms, example Such as carbon atom, nitrogen-atoms, oxygen atom, silicon atom bonding.Nitrogen-carbon-oxygen bond is similarly defined.

As comprising nitrogen-carbon-sulfide linkage and/or nitrogen-carbon-oxygen bond group, knot represented by following formula can be preferably enumerated Structure unit.

(in formula, R¹It is after removing 2 isocyanate group (- NCO) for constituting the polyisocyanates in polyisocyanates Residue or be from polyisothiocyanates remove constitute the polyisothiocyanates 2 isothiocyanate groups (- NCS) after Residue,

X²And Y²Oxygen atom or sulphur atom are each independently represented,

X in one structural unit²And Y²In 1 the above are sulphur atoms.)

(in formula, R³And R⁴Each independently represent aliphatic group or aromatic group, 2 or more R³And R⁴It can phase It is same to can also be different,

X³Indicate oxygen atom or sulphur atom.)

Containing in molecule with this structural unit resin resin combination can play greatly improve it is close with metal The effect of conjunction property.In addition, due to its refractive index height, thus it is also effective to the improvement of the physical properties of coatings such as glossiness.

Characteristic when as formation film, heat resistance is one of key property.Specifically, can be to contain 5% heat to lose The resin combination for the resin that degree of reviewing is 250 DEG C or more or 300 DEG C or more.Under 5% thermal weight loss temperature described herein refers to State temperature: under the inert gas atmospheres such as nitrogen, helium, argon, when resin is heated in the furnace that temperature rises 10 DEG C per minute, relatively The temperature of furnace when at the time of the weight that the weight resin under room temperature (20 DEG C~30 DEG C) confirms 5% being reduced, usually can be with It is measured used as the commercially available device of thermogravimetric analyzer.

For the resin combination of effect for playing heat resistance, according to its main chain backbone, bonding pattern, molecular weight, The difference for facilitating content of the key of heat-resisting sex expression etc. has various.From bonding pattern aspect, it is above-mentioned it In, it preferably comprises with knot represented by above-mentioned formula (6)~(8), (11)~(14), (41), (42), (45), (46) or (47) The resin combination of the resin of structure unit.

The number-average molecular weight of resin is preferably 500 or more, more preferably 1000 or more, further preferably 5000 or more. In general, molecular weight is higher, then the tendency better with heat resistance；On the other hand, in the case where molecular weight is excessively high, from shape It is sometimes unfavorable to set out in terms of treatability (with the Combination, mobility, ductility of other ingredients etc.) when at film, because And number-average molecular weight is preferably 1,000,000 or less, more preferably 500,000 or less, further preferably 200,000 or less.It is described herein Number-average molecular weight is following calculated value: using having the solidifying of column that at least one exclusion limit molecular weight is 10,000,000 or more Glue penetration chromatography is measured, and using standard substances such as polystyrene, will be converted into molecular weight the retention time, and thus be counted It calculates.Those skilled in the art can easily find out number-average molecular weight.It will calculate after except the peak of solvent.

The content for facilitating the key of heat-resisting sex expression is also related with above-mentioned number-average molecular weight Mn.By the number-average molecular weight of resin Divided by the quantity for constituting nitrogen-carbon-sulfide linkage sulphur atom quantity and constituting nitrogen-carbon-oxygen bond oxygen atom for including in every 1 molecule n¹Obtained from value (Mn/n¹) it is preferably 300 or less, more preferably 200 or less, further preferably 150 or less.As described above, The resin combination of present embodiment can also have effect in terms of the adaptation with metal, from show this effect in terms of Consider, it is also preferred that having more above-mentioned key in every 1 molecule resin.On the other hand, when resin has excessive above-mentioned key, especially It is that resin has above-mentioned formula (6)~(8), (11)~(14), (41), (42), (45), structural unit represented by (46) or (47) When, the flexibility as one of film performance can be also damaged sometimes.From the aspect of this, Mn/n¹Preferably 50 or more, more excellent It is selected as 70 or more.n¹Such as can calculate as follows: for example by infrared absorption spectrum or¹H-NMR etc. finds out per unit weight The quantity X of the key of (1g) resin¹(unit mol/g), according to formula: n¹=MnX¹It is calculated by above-mentioned number-average molecular weight (Mn). In the case that resin includes nitrogen-both carbon-sulfide linkage and nitrogen-carbon-oxygen bond, n¹Be constitute each key sulphur atom and oxygen atom it is total Number.

As described above, the resin for including in the resin combination of present embodiment is characterized in that constituting the key of strand The skeleton structure each key is not particularly limited in (structural unit).In particular, it is preferred that using from this reality illustrated below Apply the skeleton structure of raw material compound used in the manufacturing method of the resin combination of mode.

In such resin, containing above-mentioned formula (6)~(8), (11)~(14), (41), (42), (45), (46) or (47) characteristic of the resin of the structural unit represented by well it is preferable to use.In the following, being illustrated to these resins.

" resin with heterocycle "

Preferred 1st resin is 1 valence represented by being selected from 2 or more by above-mentioned formula (6)~(8) in present embodiment The resin of at least one of the group of group composition structural unit., it is surprising that having above-mentioned formula (6)~(8) represented Structural unit resin heat resistance it is high, adaptation, particularly the excellent adhesion with metal surface.This effect can be played Principle it is not yet clear, but the present inventor speculate may be the knot since the ring structure with conjugated system facilitates heat resistance Thiol base (- SH base) possessed by the structural unit of the sulphur atom, particularly above-mentioned formula (6) that include in structure unit can play raising The effect of adaptation.From the aspect of this, structural unit represented by above-mentioned formula (6) and/or above-mentioned formula (7) institute are preferably comprised The resin of the structural unit of expression.

In this way, the resin of present embodiment is characterized in that the bonding pattern for including in its molecule, other than the bonding Skeleton structure is not particularly limited, and preferred mode is as follows.

The content for facilitating the key of heat-resisting sex expression is also related with above-mentioned number-average molecular weight Mn.By the number-average molecular weight of resin Divided by the quantity for constituting nitrogen-carbon-sulfide linkage sulphur atom quantity and constituting nitrogen-carbon-oxygen bond oxygen atom for including in every 1 molecule n¹Obtained from value (Mn/n¹) it is preferably 300 or less, more preferably 200 or less, further preferably 150 or less.As described above, The resin combination of present embodiment can also have effect in terms of the adaptation with metal, from show this effect in terms of Consider, it is also preferred that having more above-mentioned key in every 1 molecule resin.On the other hand, when resin has excessive above-mentioned key, especially It is that resin has above-mentioned formula (6)~(8), (11)~(14), (41), (42), (45), structural unit represented by (46) or (47) When, the flexibility as one of film performance can be also damaged sometimes.From the aspect of this, Mn/n¹Preferably 50 or more, more excellent It is selected as 70 or more.n¹Such as can calculate as follows: for example by infrared absorption spectrum or¹H-NMR etc. finds out per unit weight The quantity X of the key of (1g) resin¹(unit mol/g), according to formula: n¹=MnX¹It is calculated by above-mentioned number-average molecular weight (Mn). In the case that resin includes nitrogen-both carbon-sulfide linkage and nitrogen-carbon-oxygen bond, n¹Be constitute each key sulphur atom and oxygen atom it is total Number.In the case that resin has the structural unit of formula (6)~(8), formula (6)~(8) for including in every 1 molecule resin are represented The sum of the quantity of structural unit be n₂When, Mn/n₂It is 50 or more 300 or less.n₂Pass through formula: n₂=X₂Mn is calculated.X₂It is every The sum of quantity of structural unit represented by formula (6)~(8) for including in the 1g resin, can by with X¹Same method is asked Out.

The structure being arranged between above structure unit is not particularly limited, preferably carbon atom number be 1~25 fat Race's group, the aromatic group that carbon atom number is 6~25.Specifically, for from methane, ethane, propane, butane, pentane, oneself Alkane, octane, decane, dodecane, octadecane, hexamethylene, cyclooctane, dimethyl cyclohexane, diethyl cyclohexane, 3-methyl cyclohexanol Alkane, trimethylethyl hexamethylene, dicyclohexyl methyl hydride, tetramethyl dicyclohexyl methyl hydride, benzene,toluene,xylene, ethylbenzene, diethyl Residue obtained from 2 hydrogen atoms is removed in benzene, diphenyl methane, tetramethyl diphenyl methane etc..It should be noted that depositing It also include the isomers in the case where isomers.

Among these, preferably there is the resin of structure represented by following formula (301)~(306).

(in formula, i indicates 1~12 integer, can be 1~10.)

The resin that preferred 1st resin of present embodiment is obtained preferably through following methods, this method includes following Step: the change of at least one of group that 1 valence group represented by making with being selected from by following formula (1)~(5) forms functional group It closes object and is selected from least one of monoisocyanates, polyisocyanates, monoisothiocyanates and polyisothiocyanates compound It is reacted.

-OH (1)-NH₂ (2)

In this specification, group represented by above-mentioned formula (1) is known as hydroxyl sometimes, by base represented by above-mentioned formula (2) Group is known as amino, and group represented by above-mentioned formula (3) is known as hydrazide group, group represented by above-mentioned formula (4) is known as amino Group represented by above-mentioned formula (5) is known as sulfo-amino urea groups by urea groups.The group of formula (2) as with formula (3)~(5) base The different group of group is defined.

In the following, being illustrated to the example of the manufacturing method of preferred 1st resin of present embodiment.

[it is preferable to use compound]

To in the group for selecting free hydroxyl, amino, hydrazide group, amino urea groups and sulfo-amino urea groups composition with 2 or more The compound of at least one group be not particularly limited, as long as selecting free hydroxyl (- OH), amino (- NH comprising 2 or more₂)、 Hydrazide group (- C (=O)-NH-NH₂), amino urea groups (- NH-C (=O)-NH-NH₂), sulfo-amino urea groups (- NH-C (=S)-NH- NH₂) composition at least one of group group.For example, compound represented by following formula (70) or formula (71) can be used.

(in formula, R¹²、R¹³And R¹⁴Each independently represent organic group, R¹⁵Indicate organic group or singly-bound, A¹And E¹Respectively Group from the group for independently indicating that free hydroxyl, amino, hydrazide group, amino urea groups, sulfo-amino urea groups is selected to form, B¹With D¹Each independently represent select free hydroxyl, amino, hydrazide group, amino urea groups, sulfo-amino urea groups composition group in group, Organic group or hydrogen atom, F¹Indicate hydrogen atom or organic group, d indicates 2~1000 integer, e indicate 1~3 it is whole Number, x indicate that 1 or more integer, y indicate 0 or 1 or more integer.2 or more R in same molecule¹²、R¹³、R¹⁴、A¹、E¹、 B¹、D¹、F¹And e can be the same or different respectively.

In above-mentioned formula, R¹²Preferably carbon atom number be 1~25 aliphatic group, have aromatic group (aromatic series Close object) replace carbon atom number be 7~25 aliphatic group or carbon atom number be 6~25 aromatic group.R¹²Tool Body example be from methane, ethane, propane, butane, pentane, hexane, octane, decane, dodecane, octadecane, hexamethylene, cyclooctane, Dimethyl cyclohexane, diethyl cyclohexane, trimethyl-cyclohexane, trimethylethyl hexamethylene, dicyclohexyl methyl hydride, tetramethyl two 1 is removed in cyclohexyl-methane, benzene,toluene,xylene, ethylbenzene, diethylbenzene, diphenyl methane, tetramethyl diphenyl methane etc. Residue after hydrogen atom.In this specification, " aliphatic group that the carbon atom number with aromatic group substitution is 7~25 " is Combined group including aromatic group and aliphatic group, aromatic group and aliphatic group include sometimes oxygen atom, The hetero atoms such as nitrogen-atoms, sulphur atom, the sum for the carbon atom for including in the group are 7~25.Other same terms are also the same Ground is defined.

In above-mentioned formula, R¹³And R¹⁴Preferably carbon atom number be 2~25 aliphatic group, with aromatic group replace Carbon atom number be 7~25 aliphatic group or carbon atom number be 8~25 aromatic group.R¹³And R¹⁴Concrete example For from ethane, propane, butane, pentane, hexane, octane, decane, dodecane, octadecane, hexamethylene, cyclooctane, dimethyleyelohexane Alkane, diethyl cyclohexane, trimethyl-cyclohexane, trimethylethyl hexamethylene, dicyclohexyl ethane, ethylbenzene, diethylbenzene, diphenyl The residue after 3 hydrogen atoms is removed in ethane, tetramethyl diphenylethane etc..

In above-mentioned formula, R¹⁵It indicates organic group or singly-bound, be carbon atom number is 1~25 for organic group Alkylidene, carbon atom number be 6~25 aromatic hydrocarbyl or following formula (72) or formula (73) represented by group.

(in formula, R¹⁶、R¹⁷And R¹⁸Each independently representing alkylidene, carbon atom number that carbon atom number is 1~10 is 6~10 Aromatic hydrocarbyl or singly-bound, z indicate 1~10 integer.)

R¹⁵When being the alkylidene that carbon atom number is 1~25 or the aromatic hydrocarbyl that carbon atom number is 6~25, R¹⁵Specially From methane, ethane, propane, butane, propane, hexane, octane, decane, dodecane, octadecane, hexamethylene, cyclooctane, dimethyl Hexamethylene, diethyl cyclohexane, trimethyl-cyclohexane, trimethylethyl hexamethylene, dicyclohexyl methyl hydride, tetramethyl dicyclohexyl 2 hydrogen atoms are removed in methane, benzene,toluene,xylene, ethylbenzene, diethylbenzene, diphenyl methane, tetramethyl diphenyl methane etc. Residue afterwards.

R¹⁵For singly-bound expression, R¹⁵Exist not as group, but R¹³With E¹It is bonded.In the following, in this manual Described " singly-bound " is equally defined and is used.

In above-mentioned formula (72) and formula (73), R¹⁶、R¹⁷And R¹⁸Preferably from methane, ethane, propane, butane, pentane, hexane, Octane, decane, dodecane, octadecane, hexamethylene, cyclooctane, dimethyl cyclohexane, diethyl cyclohexane, trimethyl-cyclohexane, Trimethylethyl hexamethylene, dicyclohexyl methyl hydride, tetramethyl dicyclohexyl methyl hydride, benzene,toluene,xylene, ethylbenzene, diethylbenzene, The residue after 2 hydrogen atoms is removed in diphenyl methane, tetramethyl diphenyl methane etc..There are in the case where isomers, also wrap Include the isomers.

In above-mentioned formula (71), B¹、D¹And F¹In the case where organic group, the organic group be preferably carbon atom number be 1~ Group represented by 25 alkyl, the aromatic hydrocarbyl that carbon atom number is 6~25 or following formula (74)~(76).

(in formula, R¹⁹、R²⁰、R²¹Each independently representing alkylidene that carbon atom number is 1~10 or carbon atom number is 6 ~10 aromatic group, z indicate 1~10 integer.)

In above-mentioned formula (74)~(76), R¹⁹、R²⁰And R²¹Preferably carbon atom number be 1~25 alkylidene or carbon atom The aromatic hydrocarbyl that number is 6~25.R¹⁹、R²⁰And R²¹Specially from methane, ethane, propane, butane, pentane, hexane, octane, the last of the ten Heavenly stems Alkane, dodecane, octadecane, hexamethylene, cyclooctane, dimethyl cyclohexane, diethyl cyclohexane, trimethyl-cyclohexane, trimethyl Ethyl cyclohexane, dicyclohexyl methyl hydride, tetramethyl dicyclohexyl methyl hydride, benzene,toluene,xylene, ethylbenzene, diethylbenzene, diphenyl The residue after 2 hydrogen atoms is removed in methane, tetramethyl diphenyl methane etc..There are in the case where isomers, also include that this is different Structure body.

It is illustrated below comprising selecting in free hydroxyl, amino, hydrazide group, amino urea groups and the group of sulfo-amino urea groups composition The concrete example of the compound of at least one functional group.

There is the compound of hydroxyl as (a), the polyalcohols such as ethylene glycol, propylene glycol, pentaerythrite and tool can be exemplified There is the polyalcohol of repetitive unit.

As the example of polyalcohol, acrylic polyol, polyolefin polyhydric alcohol, polyvinyl alcohol etc. can be enumerated.Acrylic acid Polyalcohol can be by making the single substance or mixture and can be total with it of the monomer of the unsaturated bond containing ethylenic bond with hydroxyl Single substance or the mixture copolymerization of the monomer of poly- other unsaturated bonds containing ethylenic bond obtain.

As the monomer of the unsaturated bond containing ethylenic bond with hydroxyl, for example, hydroxy-ethyl acrylate, acrylic acid Hydroxypropyl acrylate, hy-droxybutyl, hydroxyethyl methacrylate, hydroxy propyl methacrylate, methacrylate etc..It is preferred that For hydroxy-ethyl acrylate, hydroxyethyl methacrylate.

As the monomer for the other unsaturated bonds containing ethylenic bond that can be copolymerized with above-mentioned monomer, acrylic acid first can be enumerated Ester, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, the just own ester of acrylic acid, The acrylate such as cyclohexyl acrylate, acrylic acid-2-ethyl caproite, lauryl acrylate, benzyl acrylate, phenyl acrylate； The positive fourth of methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, methacrylic acid Base, Isobutyl methacrylate, the just own ester of methacrylic acid, cyclohexyl methacrylate, methacrylic acid -2- ethylhexyl, The methacrylates such as lauryl methacrylate, benzyl methacrylate, phenyl methacrylate；Acrylic acid, metering system The unsaturated carboxylic acids such as acid, maleic acid, itaconic acid；Acrylamide, Methacrylamide, N,N methylene bis acrylamide, acetyl The unsaturated amides such as acetone acrylamide, acetylacetone,2,4-pentanedione Methacrylamide, maleic amide, maleimide；And methyl-prop The ethylene base system list such as olefin(e) acid acid glycidyl ester, styrene, vinyltoluene, vinyl acetate, acrylonitrile, dibutyl fumarate Body；Vinyltrimethoxysilane, vinyl methyl dimethoxysilane, γ-(methyl) acryloxypropyl trimethoxy Silane etc. has the vinyl monomer etc. of hydrolyzable silyl group.

As polyolefin polyhydric alcohol, for example, with the polybutadiene of 2 or more hydroxyls, hydrogenated butadiene polymer, Polyisoprene, hydrogenated polyisoprene etc..(hereinafter hydroxyl is flat for hydroxyl value possessed by 1 molecule of statistics of polyalcohol Mean) it is preferably 2 or more.By making 2 or more the average number of hydroxyl of polyalcohol, the crosslinking for being able to suppress obtained film is close The reduction of degree.

It as polyvinyl alcohol, can enumerate: polyvinylesters obtained from vinyl esters is polymerize being saponified and is obtained The polyvinyl alcohol arrived；The modified polyvinylalcohol obtained from the main chain graft copolymerization comonomer of polyvinyl alcohol；To making vinyl Modified poly ethylene base ester obtained from ester and comonomer are copolymerized carries out being saponified manufactured modified polyvinylalcohol；It will not change It is so-called that the aldehydes such as a part formaldehyde of the hydroxyl of property polyvinyl alcohol or modified polyvinylalcohol, butyraldehyde, benzaldehyde are crosslinked Polyvinyl acetal resin etc..

Above-mentioned vinyl esters used in manufacture as polyvinyl alcohol, for example, vinyl acetate, formic acid second Enester, vinyl propionate, vinyl butyrate, new vinyl acetate acid, tertiary ethylene carbonate, vinyl laurate, vinyl stearate Ester, vinyl benzoate etc..Wherein, consider from the ease of manufacturing of polyvinyl alcohol, accessibility, cost etc., preferably Vinyl acetate.In addition, above-mentioned comonomer used in the manufacture of modified polyvinylalcohol is mainly with the modification of polyvinyl alcohol For the purpose of be copolymerized, use in the range of not damaging purport of the invention.As such comonomer, such as can be with Enumerate the olefines such as ethylene, propylene, 1- butylene, isobutene；Acrylic acid or its salt；Methyl acrylate, ethyl acrylate, acrylic acid Propyl ester (including isomers), butyl acrylate (including isomers), 2-ethyl hexyl acrylate (including isomers), lauryl base The esters of acrylic acid such as ester (including isomers)；Methacrylic acid or its salt；Methyl methacrylate, ethyl methacrylate, first Base propyl acrylate (including isomers), butyl methacrylate (including isomers), 2-Propenoic acid, 2-methyl-, octyl ester (including isomery Body), lauryl methacrylate (including isomers), the methyl-props such as octadecyl methacrylate (including isomers) Olefin(e) acid esters；Acrylamide, N methacrylamide, N- ethyl acrylamide, N, N- dimethacrylamide, diacetone acrylamide Amide, acrylamide propane sulfonic acid or its salt, acrylamide propyl dimethylamine or its salt, N hydroxymethyl acrylamide or derivatives thereof Equal acrylamide derivatives；Methacrylamide, N- methyl methacrylamide, N- ethyl methacrylamide, metering system Amide propane sulfonic acid or its salt, Methacrylamide diemethylamine or its salt, N- methylol methacrylamide or derivatives thereof Etc. methacrylamide derivatives；The N- vinyl such as N- vinyl formamide, N- vinyl acetamide, n-vinyl pyrrolidone Amides；Methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl-ethylene base ether, n-butyl vinyl base The vinyl ethers such as ether, isobutyl vinyl ether, tert-Butyl vinyl ether, dodecyl vinyl, stearyl vinyl ethers； The nitriles such as acrylonitrile, methacrylonitrile；The ethylene halides class such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride；Acetic acid The allyl compounds such as allyl ester, allyl chloride；Maleic acid or its salt or ester；Itaconic acid or its salt or ester；Vinyl three The vinyl silyl groups compound such as methoxy silane；Isopropyl acetate alkenyl esters etc..Wherein, preferably alpha-olefin is (for example, carbon atom The alpha-olefin etc. that number is 2~30), unsaturated carboxylic acid or derivatives thereof, unsaturated sulfonic acid or derivatives thereof, more preferable alpha-olefin, Particularly preferred ethylene.Based on the molal quantity for the entire infrastructure unit for constituting modified polyvinylalcohol, it is based on altogether in modified polyvinylalcohol The modified amount of polycondensation monomer is preferably 15 moles of % or less, more preferably 5 moles of % or less.

In polyalcohol enumerated above, preferably acrylic polyol, polyester polyol.

There is the concrete example of the compound of amino as (b), ethylenediamine, propane diamine, butanediamine, triethylene can be enumerated Diamines, 1,6- hexamethylene diamine, 4,4 '-diamino-dicyclohexyl methanes, piperazine, 2- methyl piperazine, isophorone diamine, norcamphane two Bis- (3- amino-benzene oxygen) benzene of amine, phenylenediamine, 4,4 '-benzidines, 1,3-, 3,3 '-diaminodiphenylsulfones, diethyltoluene The Diamines such as diamines, dianil, bis hexamethylene triamine, diethylenetriamines, trien, tetren, five Methylene hexamine, 4 sub-propyl-5-amine etc. have the polynary amine of chain, six azepine of 1,4,7,10,13,16- of 3 or more amino Ring octadecane, 1,4,7,10- tetraazacyclododecane decane, 1,4,8,12- tetraazacyclododecane pentadecane, 1,4,8,11- tetraazacyclododecane 14 The polymer shapes such as the cyclic polyols such as alkane amine, polyallylamine, polyvinylamine, polyamine represented by following formula (77)~(80) are more First amine.Wherein, preferably polyallylamine, polyvinylamine.It should be noted that polyallylamine, polyvinylamine can be used by existing There is arbitrary substance manufactured by well known method, degree of polymerization etc. is not particularly limited.Alternatively, it is also possible to for other monomers Copolymer.

(in formula, g ' indicates 2~70 integer.)

(in formula, h ' indicates 2~40 integer,

I ', j ' respectively indicate 1~6 integer, the integer that the sum of i ' and j ' are 2~7.)

(in formula, R³⁵Indicate the group in the group being made of hydrogen atom, methyl and ethyl,

S indicates 0 or 1 integer,

R, t, u respectively indicate 0 or 1 or more integer,

R and the sum of t and u are 5~90.)

There is the compound of hydrazide group as (c), for example, careless acid dihydrazide, acid dihydrazide, glutaric acid Two hydrazides, amber acid dihydrazide, adipic dihydrazide, sebacic dihydrazide etc. have the saturated dicarboxylic acid of 2~18 carbon atoms Two hydrazides；Two hydrazides of Mono-olefinics unsaturated dicarboxylic such as Malaysia acid dihydrazide, two hydrazides of fumaric acid, two hydrazides of itaconic acid；Make Polyhydrazide obtained from oligomer with lower alkyl carboxylic ester base is reacted with hydrazine or hydrazine hydrate etc..Alternatively, it is also possible to for The monomer that makes the unsaturated bond containing ethylenic bond with hydroxyl, such as hydroxy-ethyl acrylate, hydroxypropyl acrylate, acrylic acid hydroxyl fourth Ester, hydroxyethyl methacrylate, hydroxy propyl methacrylate, methacrylate etc. polymer (or copolymerization Object) with hydrazine reaction obtained from polymer, can also be to make vinyl esters (for example, vinyl acetate, vinyl formate, propionic acid Vinyl acetate, vinyl butyrate, new vinyl acetate acid, tertiary ethylene carbonate, vinyl laurate, stearic acid vinyl ester, benzoic acid Vinyl acetate etc.) polymer (or copolymer) and hydrazine reaction obtained from polymer.

There is the compound of amino urea groups as (d), for example, double semicarbazides；Make hexamethylene diisocyanate Or the diisocyanate such as isophorone diisocyanate or polyisocyanate compound and N as derived from it, N- dimethylhydrazine etc. N, N- replace multifunctional semicarbazides obtained from hydrazine or foregoing illustrative hydrazine reaction etc..

There is the compound of sulfo-amino urea groups as (e), for example, double thiosemicarbazides；Make hexa-methylene two The diisothio-cyanates such as isothiocyanates or isophorone diisothio-cyanate or polyisothiocyanates compound as derived from it Replace multifunctional thiosemicarbazide obtained from hydrazine or foregoing illustrative hydrazine reaction etc. with N, the N, N- such as N- dimethylhydrazine.

Polyalcohol cited by example as the compound with hydroxyl can for polyester polyol, polyether polyol, Fluorine polyalcohol, polycarbonate polyol, polyurethane polyol.

As polyester polyol, for example: make selected from succinic acid, adipic acid, decanedioic acid, dimeric dibasic acid, maleic acid The single substance or mixture of binary acid in the group of the carboxylic acids such as acid anhydride, phthalic anhydride, M-phthalic acid, terephthalic acid (TPA) with The single substance of polyalcohol in group selected from ethylene glycol, propylene glycol, diethylene glycol (DEG), neopentyl glycol, trimethylolpropane, glycerol etc. Or polyester polyol obtained from the condensation reaction of mixture；And, for example, the open loop of the 6-caprolactone by using polyalcohol Poly caprolactone obtained from polymerization etc..

As polyether polyols alcohols, comprising: strong using the hydroxide such as lithium, sodium, potassium, alcoholates, alkylamine etc. Basic catalyst, single substance or mixture addition of ethylene oxide, propylene oxide, epoxy butane to multi-hydroxy compound, Polyether polyols alcohols obtained from the single substance or mixture of the epoxyalkane such as 7-oxa-bicyclo[4.1.0, styrene oxide；Make second two Polyether polyols alcohols obtained from the polyfunctional compounds such as amine react with epoxyalkane；And using these polyethers as medium By so-called polymer polyol alcohols obtained from the polymerization such as acrylamide；Etc..

As multi-hydroxy compound, can enumerate

(1) diglycerol, double trimethylolpropane, pentaerythrite, dipentaerythritol etc.,

(2) erythrite, D- threitol, L-arabinose alcohol, ribitol, xylitol, D-sorbite, mannitol, galactolipin The sugar alcohols such as alcohol, rhamnitol based compound,

(3) arabinose, ribose, xylose, glucose, mannose, galactolipin, fructose, sorbose, rhamnose, fucose, The monosaccharides such as deoxyribose,

(4) disaccharides such as trehalose, sucrose, maltose, cellobiose, gentiobiose, lactose, melibiose,

(5) three carbohydrate such as raffinose, gentianose, melezitose,

(6) four carbohydrate such as stachyose, etc..

Fluorine-containing polyalcohol is the polyalcohol that intramolecular contains fluorine, including such as Japanese Unexamined Patent Application 57-34107 bulletin, day Fluoroolefin disclosed in this tekiaki 61-275311 bulletin, cyclic vinyl ether, hydroxyalkyl vinylether, monocarboxylic acid ethylene The copolymer of ester etc..

As polycarbonate polyol class, can enumerate the dialkyl carbonates such as dimethyl carbonate, ethylene carbonate etc. In the low molecule carbonate products of the diaryl carbonates such as alkylene carbonate, diphenyl carbonate etc and above-mentioned polyester polyol Substance obtained from the low molecular polylol polycondensation used.

Polyurethane polyol by conventional method, for example can be such that polyalcohol reacts with polyisocyanates to obtain.As Polyalcohol without carboxyl, the substance of low molecular weight, which can arrange, shows ethylene glycol, propylene glycol etc., and the substance of high molecular weight can illustrate Acrylic polyol, polyester polyol, polyether polyol etc. out.

It can have the group that free hydroxyl, amino, hydrazide group, amino urea groups and sulfo-amino urea groups composition are selected comprising one In the compound of repetitive unit of 1 group be compound represented by following formula (81).

R²²-A¹ (81)

(in formula, R²²Indicate organic group,

A¹Indicate group defined in above-mentioned formula (70).)

In above-mentioned formula, R²²Preferably carbon atom number be 1~25 aliphatic group, carbon atom number be 7~25 with virtue The aliphatic group of fragrant race's group substitution, the aromatic group that carbon atom number is 6~25.Specifically, R²²It is from methane, second Alkane, propane, butane, pentane, hexane, octane, decane, dodecane, octadecane, hexamethylene, cyclooctane, dimethyl cyclohexane, two Ethyl cyclohexane, trimethyl-cyclohexane, trimethylethyl hexamethylene, dicyclohexyl methyl hydride, tetramethyl dicyclohexyl methyl hydride, benzene, The residue after 1 hydrogen atom is removed in toluene, dimethylbenzene, ethylbenzene, diethylbenzene, diphenyl methane, tetramethyl diphenyl methane etc.. There are in the case where isomers, also include the isomers.

As compound represented by above-mentioned formula (81), specifically, methanol, ethyl alcohol, propyl alcohol, butanol, penta can be enumerated Alcohol, hexanol, octanol, decyl alcohol, dodecanol, octadecanol, cyclohexanol, Lotka-Volterra circle system, dimethyl cyclohexanol, diethyl cyclohexanol, Cyclonol, trimethylethyl cyclohexanol, dicyclohexyl methanol, tetramethyl dicyclohexyl methanol, phenol, methylphenol, The hydroxy compounds such as dimethlbenzene, ethyl -phenol, diethyl phenol；Ethamine, propylamine, butylamine, amylamine, hexylamine, octylame, decyl amine, Dodecyl amine, cyclohexylamine, cyclooctylamine, dimethyl cyclohexyl amine, phenyl amine, aminomethyl phenyl amine, 3,5-dimethylphenyl amine, ethylphenyl The amine such as amine, diethyl phenyl amine；Ethylhydrazide, propyl hydrazides, butyl hydrazides, amyl hydrazides, hexyl hydrazides, octyl hydrazides, the last of the ten Heavenly stems Base hydrazides, dodecyl hydrazides, cyclohexyl hydrazides, cyclooctyl hydrazides, Dimethylcyclohexyl hydrazides, phenyl hydrazide, aminomethyl phenyl The hydrazides such as hydrazides, 3,5-dimethylphenyl hydrazides, ethylphenyl hydrazides, diethyl phenyl hydrazides；Ethylamino urea, propylcarbamic urea, Butylamino urea, pentyl amino urea, hexylamino urea, octyl amino urea, Decylamino urea, dodecylamino urea, cyclohexyl Semicarbazides, cyclooctyl semicarbazides, Dimethylcyclohexyl semicarbazides, Carbaphen, MethYlphenylamino urea, 3,5-dimethylphenyl ammonia The semicarbazides such as base urea, ethylphenyl semicarbazides, diethyl phenyl semicarbazides；Ethylenebis dithiocarbamate semicarbazides, propyl dithiocarbamate semicarbazides, fourth Base thiosemicarbazide, pentylthio semicarbazides, hexyl thiosemicarbazide, octylsulfo semicarbazides, decyl thiosemicarbazide, 12 Alkylthio semicarbazides, cyclohexyl thio semicarbazides, cyclooctyl thiosemicarbazide, Dimethylcyclohexyl thiosemicarbazide, phenyl Thiosemicarbazide, aminomethyl phenyl thiosemicarbazide, 3,5-dimethylphenyl thiosemicarbazide, ethylphenyl thiosemicarbazide, diethyl The thiosemicarbazides such as phenyl semicarbazides.

Compound represented by above-mentioned formula (81) can be compound represented by following formula (82).

R²³-R¹⁵-E¹ (82)

(in formula,

R²³Indicate that carbon atom number is 1~25 unsaturated fatty hydrocarbons base,

R¹⁵、E¹Indicate group defined in above-mentioned formula (71).)

Compound represented by above-mentioned formula (82) is more preferably compound represented by following formula (83)~(85).

(in formula,

R²⁴、R²⁵And R²⁶The saturated hydrocarbyl that hydrogen atom or carbon atom number are 1~6 is each independently represented,

R²⁷、R²⁸、R²⁹And R³⁰Each independently represent hydrogen atom, the saturated hydrocarbyl that carbon atom number is 1~6,

R³¹Indicate that carbon atom number is 1~6 saturated hydrocarbyl or singly-bound, E¹Indicate group defined in above-mentioned formula (71),

W indicates 1~3 integer.)

Isothiocyanate compound is the compound in 1 molecule with 1 or more isothiocyanate group, is classified as Dan Yi Thiocyanates and polyisothiocyanates.

In the resin combination of present embodiment, monoisothiocyanates is the change in 1 molecule with 1 isothiocyanate group Close object, preferably compound represented by following formula (30).

R⁵-NCS (30)

(in formula, R⁵Indicate organic group.)

In above-mentioned formula (30), R⁵Preferably carbon atom number be 1~25 aliphatic group or carbon atom number be 6~25 virtue Fragrant race's group.R⁵It can be the aliphatic group that the carbon atom number replaced with aromatic group is 7~25.Specifically, R⁵It is From methane, ethane, propane, butane, pentane, hexane, octane, decane, dodecane, octadecane, hexamethylene, cyclooctane, dimethyl Hexamethylene, diethyl cyclohexane, trimethyl-cyclohexane, trimethylethyl hexamethylene, dicyclohexyl methyl hydride, tetramethyl dicyclohexyl 1 hydrogen atom is removed in methane, benzene,toluene,xylene, ethylbenzene, diethylbenzene, diphenyl methane, tetramethyl diphenyl methane etc. Residue afterwards.There are in the case where isomers, also include the isomers.

Specifically, compound represented by above-mentioned formula (30) can enumerate methane isothiocyanates, ethane isothiocyanic acid Ester, propane isothiocyanates, butane isothiocyanates, pentane isothiocyanates, hexane isothiocyanates, octane isothiocyanic acid Ester, decane isothiocyanates, dodecane isothiocyanates, octadecane isothiocyanates, hexamethylene isothiocyanates, cyclooctane are different Thiocyanates, dimethyl cyclohexane isothiocyanates, diethyl cyclohexane isothiocyanates, trimethyl-cyclohexane isothiocyanic acid Ester, trimethylethyl hexamethylene isothiocyanates, dicyclohexyl methyl hydride isothiocyanates, the different sulphur cyanogen of tetramethyl dicyclohexyl methyl hydride Acid esters, phenyl isothiocyanate, Tolueneisothiocyanate, diformazan PhNCS, ethylbenzene isothiocyanates, the different sulphur of diethylbenzene Cyanate, diphenyl methane isothiocyanates, tetramethyl diphenyl methane isothiocyanates etc..

Compound represented by above-mentioned formula (30) can be compound represented by following formula (86).

R²³-R¹⁵-NCS (86)

(in formula, R¹⁵、R²³Indicate group defined in above-mentioned formula (82).)

Compound represented by above-mentioned formula (30) is more preferably compound represented by following formula (87)~(89).

(in formula,

R²⁴、R²⁵And R²⁶Each independently represent hydrogen atom, the saturated hydrocarbyl that carbon atom number is 1~6,

R²⁷、R²⁸、R²⁹And R³⁰The saturated hydrocarbyl that hydrogen atom or carbon atom number are 1~6 is each independently represented,

R³¹Indicate that carbon atom number is 1~6 saturated hydrocarbyl or singly-bound,

W indicates 1~3 integer.)

As the concrete example of compound represented by formula (87)~(89), acrylic acid methyl-isorhodanate, first can be enumerated Base acrylic acid methyl-isorhodanate, acrylic acid (2- isothiocyanic acid ethyl) ester, methacrylic acid (2- isothiocyanic acid ethyl) ester, third Olefin(e) acid (3- isothiocyanic acid propyl) ester, methacrylic acid (3- isothiocyanic acid propyl) ester, 2- isothiocyanato ethyl vinyl Ether, 4- isothiocyanato butyl vinyl ether, to (isocyanatomethyl) styrene, to (isocyanatoethyl benzene second Alkene) etc..

In the resin combination of present embodiment, polyisothiocyanates is that have 2 or more isothiocyanate groups in 1 molecule Compound, for example, compound represented by following formula (32).

(in formula, R⁶Indicate organic group,

A indicates 2~1000 integer.)

Preferred 1st mode of such polyisothiocyanates is comprising repetition represented by least two following formula (33) The polymer of unit.

(in formula, R⁷Indicate organic group,

R⁸Indicate organic group or singly-bound,

B indicates 1 or more integer,

G indicates 1 or 2.2 or more R in same molecule⁷、R⁸, b and g can be the same or different respectively.)

The polymer of preferred 1st mode as the polyisothiocyanates recorded herein can have above-mentioned formula (33) institute Repetitive unit other than the repetitive unit of expression, one kind or two or more.The end of the polymer is from polymerization initiator, gathers Terminator, terminal-modified dose of group are closed, it is different due to the difference of manufacturing method, as long as the purport for not violating present embodiment It is not particularly limited.That is, preferred 1st mode of polyisothiocyanates is more preferably compound represented by following formula (90).

(in formula, R³²Indicate organic group,

R³³Indicate organic group or singly-bound,

B²And D²It each independently represents selected from by the organic group and hydrogen other than isothiocyanate group, isothiocyanate group At least one kind of group in molecular group former,

G¹~G^xExpression may include or the organic group not comprising isothiocyanate group, the integer that x is 1 or more, n_xIt indicates 1 or more integer,

G indicates 1 or 2,

F indicates 1 or more integer,

M indicates 2 or more integer.2 or more R in same molecule³²、R³³, f and g respectively can identical not yet Together.)

In above-mentioned formula (90), G¹~G^xIndicate the repetitive unit other than repetitive unit represented by above-mentioned formula (33).In addition, n_xIndicate G^xRepetitive unit quantity.For example, other than the repetitive unit represented by above-mentioned formula (43), G¹、G²、G³This 3 kinds Repetitive unit is respectively present n₁、n₂、n₃When, it is G¹n₁G²n₂G³n₃。

In above-mentioned formula (90), R³²Preferably carbon atom number be 2~25 aliphatic group, carbon atom number be 7~25 band The aromatic group that the aliphatic group or carbon atom number for having aromatic compound to replace are 8~25.R³²Concrete example be from second Alkane, propane, butane, pentane, hexane, octane, decane, dodecane, octadecane, hexamethylene, cyclooctane, dimethyl cyclohexane, two Ethyl cyclohexane, trimethyl-cyclohexane, trimethylethyl hexamethylene, dicyclohexyl ethane, ethylbenzene, diethylbenzene, diphenylethane, Tetramethyl diphenylethane, ethyl alcohol, propyl alcohol, butanol, amylalcohol, hexanol, octanol, decyl alcohol, dodecanol, octadecanol, cyclohexanol, Lotka-Volterra circle system, dimethyl cyclohexanol, diethyl cyclohexanol, cyclonol, trimethylethyl cyclohexanol, dicyclohexyl ethyl alcohol etc. The middle residue removed after 3 hydrogen atoms.

In above-mentioned formula (90), R³³Indicate organic group or singly-bound, in the case where being organic group, be carbon atom number be 1~ Group represented by 25 alkylidene, the aromatic hydrocarbyl that carbon atom number is 6~25 or following formula (91) or formula (92).

(in formula, R³⁴、R³⁶And R³⁷Each independently representing alkylidene, carbon atom number that carbon atom number is 1~10 is 6~10 Aromatic hydrocarbyl or singly-bound,

L indicates 1~10 integer.)

R³⁴Be carbon atom number be 1~25 alkylidene, carbon atom number be 6~25 aromatic hydrocarbyl when, specifically, being From methane, ethane, propane, butane, pentane, hexane, octane, decane, dodecane, octadecane, hexamethylene, cyclooctane, dimethyl Hexamethylene, diethyl cyclohexane, trimethyl-cyclohexane, trimethylethyl hexamethylene, dicyclohexyl methyl hydride, tetramethyl dicyclohexyl 2 hydrogen atoms are removed in methane, benzene,toluene,xylene, ethylbenzene, diethylbenzene, diphenyl methane, tetramethyl diphenyl methane etc. Residue afterwards.

In above-mentioned formula (91), (92), R³⁴、R³⁶And R³⁷Preferably from methane, ethane, propane, butane, pentane, hexane, pungent Alkane, decane, dodecane, octadecane, hexamethylene, cyclooctane, dimethyl cyclohexane, diethyl cyclohexane, trimethyl-cyclohexane, three Methylethylcyclohexane, dicyclohexyl methyl hydride, tetramethyl dicyclohexyl methyl hydride, benzene,toluene,xylene, ethylbenzene, diethylbenzene, two The residue after 2 hydrogen atoms is removed in phenylmethane, tetramethyl diphenyl methane etc..It should be noted that there are isomers In the case of, it further include the isomers.

In above-mentioned formula (90), B²And D²In the case where organic group, it is 1~25 which, which is preferably carbon atom number, Alkyl, carbon atom number be 6~25 aromatic hydrocarbyl or following formula (93)~(95) represented by group.

(in formula, R³⁸、R³⁹And R⁴⁰Each independently represent alkylidene that carbon atom number is 1~25 or carbon atom number be 6~ 25 aromatic group,

P indicates 1~10 integer.)

In above-mentioned formula (93)~(95), R³⁸、R³⁹And R⁴⁰Preferably carbon atom number be 1~25 alkylidene, carbon atom number be 6~25 aromatic hydrocarbyl, specifically, being from methane, ethane, propane, butane, pentane, hexane, octane, decane, 12 Alkane, octadecane, hexamethylene, cyclooctane, dimethyl cyclohexane, diethyl cyclohexane, trimethyl-cyclohexane, trimethylethyl hexamethylene Alkane, dicyclohexyl methyl hydride, tetramethyl dicyclohexyl methyl hydride, benzene,toluene,xylene, ethylbenzene, diethylbenzene, diphenyl methane, tetramethyl The residue after 2 hydrogen atoms is removed in base diphenyl methane etc..It should be noted that also including there are in the case where isomers The isomers.

1st mode of polyisothiocyanates illustrated above can for single isothiocyanic acid as represented by above-mentioned formula (41) The polymer of ester, the polymer may be the copolymer with other monomers.Specifically, can enumerate: the different sulphur cyanogen of acrylic acid The copolymer of sour methyl esters and methyl acrylate, the copolymer of methacrylic acid methyl-isorhodanate and methyl methacrylate, third The copolymer of olefin(e) acid (2- isothiocyanic acid ethyl) ester and methyl acrylate, methacrylic acid (2- isothiocyanic acid ethyl) ester and methyl Copolymer, the methacrylic acid (3- of the copolymer of methyl acrylate, acrylic acid (3- isothiocyanic acid propyl) ester and methyl acrylate Isothiocyanic acid propyl) ester and the copolymer of methyl methacrylate etc..These compounds can use well known method system It makes.

In the resin combination of present embodiment, the 2nd mode of polyisothiocyanates is following polyisothiocyanates, tool The structural unit represented by following formula (40) and in the group being made of the unit represented by following formula (41)~(47) At least one structural unit constitutes the nitrogen-atoms and carbon atom bonding of polyisothiocyanates.

SCN-R³- (40)

(in formula, R³Organic group is each independently represented,

R⁴Indicate aliphatic group or aromatic group or aliphatic alkyl or aromatic hydrocarbyl,

2 or more R³And R⁴It can be the same or different,

X³Indicate oxygen atom or sulphur atom.)

In above-mentioned formula (40), formula (41)~(47), R³Preferably aliphatic group, carbon atom of the carbon atom number for 1~25 The aromatic group that number is 6~25.Specifically, R³Be from methane, ethane, propane, butane, pentane, hexane, octane, decane, Dodecane, octadecane, hexamethylene, cyclooctane, dimethyl cyclohexane, diethyl cyclohexane, trimethyl-cyclohexane, trimethylethyl Hexamethylene, dicyclohexyl methyl hydride, tetramethyl dicyclohexyl methyl hydride, benzene,toluene,xylene, ethylbenzene, diethylbenzene, diphenyl methane, The residue after 2 hydrogen atoms is removed in tetramethyl diphenyl methane etc..There are in the case where isomers, also include the isomers.

To the group-X for including in above-mentioned formula (43), formula (45)³-R⁴It is illustrated.

As described later, in the manufacture of polyisothiocyanates of the invention, N, N '-two represented by above-mentioned formula (43) are generated N- substitution-O- represented by two thio allophanic acid keys or above-mentioned formula (45) is replaced to replace thiocarbamate base (X³For oxygen The case where atom) or N- substitution-S- substitution dithiocarbamate groups (X³The case where for sulphur atom) when, use hydroxy compound Object or thio-alcohol.Base-X³-R⁴It is the group from the hydroxy compounds or thio-alcohol, using hydroxy compounds, X³For oxygen atom, using thio-alcohol, X³For sulphur atom.

R⁴It can be alkyl.Above-mentioned alkyl has at least one of aliphatic group and aromatic group, in addition to carbon original Other than son, oxygen atom and nitrogen-atoms etc. can also be included.R⁴It is aliphatic group or aromatic group, preferably carbon atom number is The fat that the aromatic group that 1~22 aliphatic group or carbon atom number is 6~22, more preferably carbon atom number are 1~22 The aliphatic group and carbon atom number that the aromatic group or carbon atom number that race's group, carbon atom number are 1~22 are 1~22 are 6 The group that carbon atom number made of~22 aromatic group bonding is 7~22.As R⁴Concrete example, can enumerate methyl, Ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, octadecyl, cyclopenta, cyclohexyl, Suberyl, cyclooctyl, methylcyclopentyl, ethylcyclopentyl, methylcyclohexyl, ethylcyclohexyl, propylcyclohexyl, butylcyclohexyl Base, pentylcyclohexyl, hexyl cyclohexyl, Dimethylcyclohexyl, diethyl butylcyclohexyl, dibutyl cyclohexyl, phenyl, methylbenzene Base, ethylphenyl, propyl phenyl, butyl phenyl, amyl phenyl, hexyl phenyl, octyl phenyl, nonyl phenyl, cumyl phenyl, two Aminomethyl phenyl etc..

Polyisothiocyanates in present embodiment, which can be, makes a kind of the polyisothiocyanates as present embodiment Polyisothiocyanates obtained from following formula (33) compound represented further polymerize.

SCN-R³-NCS (33)

(in formula, R³Indicate organic group.)

R in above-mentioned formula (33)³Preferably carbon atom number be 1~25 aliphatic group, carbon atom number be 6~25 virtue Fragrant race's group.R³Concrete example be from methane, ethane, propane, butane, pentane, hexane, octane, decane, dodecane, octadecane, Hexamethylene, cyclooctane, dimethyl cyclohexane, diethyl cyclohexane, trimethyl-cyclohexane, trimethylethyl hexamethylene, two hexamethylenes Methylmethane, tetramethyl dicyclohexyl methyl hydride, benzene,toluene,xylene, ethylbenzene, diethylbenzene, diphenyl methane, tetramethyl diphenyl The residue after 2 hydrogen atoms is removed in methane etc..There are in the case where isomers, also include the isomers.R³Under more preferably State group represented by formula (300)~(306).

(in formula, i indicates 1~12 integer, can be 1~10.)

As compound represented by above-mentioned formula (33), may further preferably enumerate hexa-methylene diisothio-cyanate, Isophorone diisothio-cyanate, 4,4 '-dicyclohexyl methyl hydride diisothio-cyanates, 4,4 '-diphenyl methane diisothiocyanic acids Ester, toluene diisothio-cyanate (Isomers), naphthalene diisothio-cyanate (Isomers) etc..

As compound represented by above-mentioned formula (33), phenylene diisothio-cyanate, 4,4 '-two different sulphur can also be enumerated Bis- (3- isothiocyanatophenoxy) benzene of cyanic acid base diphenyl ether, 1,3-, 3,3 '-diisothiocyanic acid roots close diphenyl sulphone (DPS), diethyl Base toluene diisothio-cyanate etc..

Hereinafter, to resin (polyisothiocyanates) obtained from the polymerization of compound represented by above-mentioned formula (33) is remembered It carries.It should be noted that in following records, sometimes by compound represented by above-mentioned formula (33) with the compound before polymerizeing Meaning is denoted as " monomer ".

About the polyisothiocyanates that the polymerization by " monomer " represented by above-mentioned formula (33) manufactures, in its manufacture When, it is used using hydroxy compounds and/or thio-alcohol as auxiliary material.

As hydroxy compounds, can enumerate methanol, ethyl alcohol, propyl alcohol, butanol, amylalcohol, hexanol, enanthol, octanol, decyl alcohol, Dodecanol, cyclopentanol, cyclohexanol, suberol, Lotka-Volterra circle system, methylcyclopentanol, ethyl cyclopentanol, methyl cyclohexanol, ethyl ring Hexanol, cyclohexyl alcohol, butylcyclohexyl alcohol, amyl cyclohexanol, hexyl cyclohexanol, dimethyl cyclohexanol, diethyl cyclohexanol, two Butylcyclohexyl alcohol, phenol, methylphenol, ethyl -phenol, propylphenol, butylphenol, amyl phenol, hexylphenol, octyl benzene Phenol, nonyl phenol, cumyl phenol, xylenol, Methylethyl phenol, methyl-propyl phenol, methyl butyl phenol, methylpent Base phenol, diethyl phenol, ethyl propyl phenol, ethyl-butyl phenol, dipropyl phenol, dicumyl phenol, pseudocuminol, Triethyl group phenol, naphthols etc..

Also ethylene glycol, 1,2- propylene glycol, 1,3- propylene glycol, 1,3 butylene glycol, 1,4- butanediol, 2,3- fourth two can be used It is alcohol, 1,6-HD, neopentyl glycol, neopentyl glycol 3-hydroxypivalic acid ester, 2- ethyl -1,3- hexylene glycol, trimethylolpropane, sweet Polyester polyol, the polyether polyol of the low molecular weight compounds such as oil, 1,2,6- hexanetriol and molecular weight about 200~10,000 Deng.

As thio-alcohol, can enumerate methyl mercaptan, ethyl mercaptan, propanethiol, butanethiol, amyl hydrosulfide, hexyl mercaptan, heptanthiol, Spicy thioalcohol, decyl mercaptan, lauryl mercaptan, cyclopentanethiol, cyclohexylmercaptan, cycloheptyl mercaptan, cyclooctasulfur alcohol, methyl cyclopentanethiol, ethyl Cyclopentanethiol, methyl cyclohexane mercaptan, cyclohexyl mercaptan, cyclohexyl mercaptan, butylcyclohexyl mercaptan, amyl cyclohexylmercaptan, oneself Basic ring hexyl mercaptan, dimethyleyelohexane mercaptan, diethyl cyclohexylmercaptan, dibutyl cyclohexylmercaptan, benzenethiol, methylbenzene phenyl-sulfhydrate, second It is base benzenethiol, propyl benzenethiol, butyl benzenethiol, amyl benzenethiol, hexyl benzenethiol, octyl benzenethiol, nonyl benzenethiol, withered Base benzenethiol, thiophenol dimethyl benzene, Methylethyl benzenethiol, methyl-propyl benzenethiol, methyl butyl benzenethiol, methyl amyl benzene Thiophenol, diethylbenzene thiophenol, ethyl propyl benzenethiol, ethyl-butyl benzenethiol, dipropyl benzenethiol, dicumyl benzenethiol, three Methylbenzene phenyl-sulfhydrate, triethylbenzene thiophenol, thionaphthol etc..

In the case where using hydroxy compounds, the different sulphur of " monomer " represented by above-mentioned hydroxy compounds and above-mentioned formula (33) Cyanic acid ester group/hydroxyl equivalent ratio can be selected from 10~100 or so value according to purpose.It is also the same when using thio-alcohol, different sulphur Cyanic acid ester group/sulphur hydroxyl equivalent ratio can be selected from 10~100 or so value according to purpose.

By the polymerization reaction of the monomer of formula (33), different thiocyanuric acid ester group represented by formula (41) can be formed.As with The different thiocyanuric acid esterification catalyst of the different thiocyanuric acid ester group represented by the formula that formed (41), preferably quaternary ammonium salt, more preferably For quaternary ammonium hydroxide, quaternary ammonium carboxylic acid, further preferably quaternary ammonium carboxylic acid.As concrete example, can enumerate tetramethylammonium hydroxide, The tetra-alkyl ammonium hydroxides such as tetraethyl ammonium hydroxide, tetrabutylammonium hydroxide；Acetic acid tetramethyl ammonium, acetic acid tetraethyl ammonium salt, Organic monoacids salt such as tetrabutylphosphoniuacetate acetate ammonium salt etc..Also the alkane such as acetic acid, valeric acid, isovaleric acid, caproic acid, octanoic acid, tetradecylic acid can be used The metal salt etc. of yl carboxylic acid, from the aspect of it can reduce dosage, preferred organic monoacid salt etc..

As the hydroxy compounds for diluting above-mentioned different thiocyanuric acid esterification catalyst, it can be cited for example that methanol, ethyl alcohol, 1- Butanol, 2- butanol, 2- methyl-1-propyl alcohol, 1,2- propylene glycol, 1,3- propylene glycol, 1,3 butylene glycol, 1,4- butanediol, 2,3- fourth The phenolic hydroxyl group chemical combination such as the alcohol hydroxyl groups such as glycol, glycerol, cyclohexanol compound, phenol, cresols, dimethlbenzene, pseudocuminol Object.From the crystalline aspect of thus obtained polyisocyanates, preferably 2- butanol, 2- methyl-1-propyl alcohol, 1,3- fourth two Alcohol, 2,3- butanediol etc. have the alcohol of side chain.Alternatively, it is also possible to be mixed two or more.It should be noted that can make The hydroxy compounds is replaced with thio-alcohol.

Make monomer represented by above-mentioned formula (33) or is that isothiocyanate group has been subjected to amino first with hydroxy compounds When Esterification monomer is reacted in the presence of above-mentioned different thiocyanuric acid esterification catalyst, according to above-mentioned hydroxy compound The condition that the concentration of different thiocyanuric acid esterification catalyst after object dilution is 1~20 mass % carries out.Concentration is preferably 1~10 matter Measure %.If concentration is 1 mass % or more, the amount of associated hydroxy compounds will not become with different thiocyanuric acid esterification catalyst More, the physical property of obtained polyisothiocyanates and the film being consequently formed is difficult to decrease.If concentration is 20 mass % hereinafter, phase The co-catalysis effect of the hydroxy compounds of companion will not reduce, as a result, being difficult to cause the dosage of different thiocyanuric acid esterification catalyst Increase and the coloring of polyisothiocyanates etc..

In addition to different thiocyanuric acid esterification catalyst because in the raw materials such as monomer represented by above-mentioned formula (33) it is micro containing acid Property ingredient and except in the case of inactivating, the dosage of different thiocyanuric acid esterification catalyst is relative to the weight of monomer diisothio-cyanate 1ppm~10%, preferably 10ppm~5%.The amount can then give full play to and be esterified as different thiocyanuric acid if 1ppm or more The function of catalyst.The amount is if 3% hereinafter, then for making the acid phosphatase compound of different thiocyanuric acid esterification catalyst inactivation It is reduced with the additive amount of acid phosphoesterase compound (aftermentioned).

It can be used when reaction or do not have the molten of reactivity without using solvent, but by using with isothiocyanate group Agent, the control of reaction become to be more easier.

As the example of solvent, ethyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol list can be used The esters such as ether acetate or ethers, benzene,toluene,xylene, ethylbenzene, trimethylbenzene etc. are aromatic hydrocarbon etc..It is of course also possible to by two Kind or more solvent be used in mixed way.

Different thiocyanuric acid esterification 30 DEG C~120 DEG C, preferably 50 DEG C~100 DEG C carry out.The progress of reaction can be with Pass through reaction solution¹H-NMR analyzes to confirm.

At the time of reaction reaches desired conversion ratio, make catalyst inactivation by putting into reaction terminating agent, to stop Only react.Conversion ratio selects to be suitably preferably 10~30% in the range of 10~60%.When conversion ratio is low, it can obtain The lower polyisothiocyanates of viscosity, but from the aspect of productivity, preferably conversion ratio is 10% or more.On the other hand, if Conversion ratio is 60% hereinafter, then the viscosity of polyisothiocyanates will not become excessively high, thus preferably.

Conversion ratio can be found out by following formula.

?¹In H-NMR spectrum, the peak of the methyl of tetramethylsilane is set as 0ppm, according to the following formula by the peak of 3.5ppm The integrated value (B) at the peak of integrated value (A) and 4.8ppm calculates conversion ratio.

Conversion ratio (%)=B/ (A+B) × 100

As the terminator of different thiocyanuric acid esterification, using in acid phosphatase compound and acid phosphoesterase compound 1 kind or more of compound.

Acid phosphatase compound is inorganic acid, it can be cited for example that phosphoric acid, phosphorous acid, ortho phosphorous acid, diphosphorous acid, secondary phosphorus Acid, pyrophosphoric acid, peroxide phosphoric acid etc..Acid phosphatase compound is preferably phosphoric acid.

Acid phosphoesterase compound is the compound with acidic-group and ester group, it can be cited for example that carbon atom number is 2 ~8 monoalkyl phosphoric acid esters, monoalkyl phosphite ester or carbon atom number be 4~16 dialkyl phosphate, dialkyl group phosphorous Acid esters or didodecyl phosphate, diphenyl phosphate, mono phosphoric acid ester lauryl, phosphoric acid monophenyl, phosphorous acid dilauryl, phosphorous Diphenyl phthalate, phosphorous acid list lauryl, phosphorous acid monophenyl etc..It is 3~8 that acid phosphoesterase compound, which is preferably carbon atom number, The dialkyl phosphate that monoalkyl phosphoric acid esters or carbon atom number are 6~16, more preferably dioctylphosphoric acid ester, mono-octyl phosphate. , it is preferable to use acid phosphatase compound among these.The additive amount of acid phosphatase compound is urged relative to the esterification of different thiocyanuric acid The stoichiometry of agent is preferably 1~10 equivalent, more preferably 1~6 equivalent.Additive amount if 1 equivalent more than, can make different Thiocyanuric acid esterification catalyst sufficiently inactivates.Additive amount is if 10 equivalents hereinafter, the filtering of generated insoluble matter will not become It obtains difficult thus preferred.

The polyisothiocyanates of present embodiment can be compound represented by following formula (96)~(99).

(in formula, h ' indicates 2~40 integer,

(in formula, k indicates 1~4 integer.)

(in formula, R³⁵Indicate the group in the group being made of hydrogen atom, methyl, ethyl,

S indicates 0 or 1 integer,

R, t, u respectively indicate that 0 or 1 or more integer, r and the sum of t and u are 5~90.)

(in formula, v indicates 2~70 integer.)

[reaction method]

To present embodiment make have select free hydroxyl, amino, hydrazide group, amino urea groups and sulfo-amino urea groups composition At least one of group group compound and isothiocyanates (can be monoisothiocyanates, or polyisocyanate sulphur cyanogen Acid esters) reaction method be illustrated.

The resin combination of present embodiment can contain all following resins.

1. making the group for selecting free hydroxyl, amino, hydrazide group, amino urea groups and sulfo-amino urea groups composition with 2 or more In at least one kind of group compound reacted with monoisothiocyanates obtained from resin；

2. making to select 1 in the group of free hydroxyl, amino, hydrazide group, amino urea groups and sulfo-amino urea groups composition with 1 Resin obtained from the compound of kind group is reacted with polyisothiocyanates；

3. making the group for selecting free hydroxyl, amino, hydrazide group, amino urea groups and sulfo-amino urea groups composition with 2 or more In at least one kind of group compound reacted with polyisothiocyanates obtained from resin.

In all cases, the combination for the functional group reacted is all the same, can according to method recited herein into Row.

In the following description, reaction equation is shown in order to should be readily appreciated that reaction, which is with monofunctional compound Example and recorded, but also similarly reacted certainly in the case where polyfunctional compound.

[with reacting for the compound with hydroxyl]

Represented by the reacting by following formula (100) of compound with hydroxyl and isothiocyanates.

(in formula, R⁴¹、R⁴²Each independently represent organic group.)

Reaction can be implemented in the presence of solvent, can also implement in the absence of solvent.About in the presence of solvent into The solvent used when row is inert solvent preferably for hydroxyl and isothiocyanate group；Although and isothiocyanate group Reaction, but the extremely slow solvent of speed for goal response.As preferred solvent, pentane, hexane, heptan can be enumerated The hydrocarbon compounds such as alkane, octane, nonane, decane, dodecane, the tetradecane, pentadecane, hexadecane, octadecane, nonadecane；Ether, four Hydrogen furans, Octyl Ether, nonyl ethers, decyl ethers, lauryl ether, myristyl ether, pentadecyl ether, cetyl ether, 18 Ethers made of the hydrocarbon compounds such as alkyl ether, tetraethyleneglycol dimethyl ether are bonded by ehter bond；Dimethyl sulphide, diethyl thioether, two fourths Base thioether, dihexyl thioether, octyl thioether, nonyl thioether, decyl thioether, dodecyl thioether, myristyl thioether, pentadecane Sulphur made of the hydrocarbon compounds such as base thioether, cetyl thioether, octadecyl thioether, nonadecyl thioether are bonded by thioether bond Ethers；Benzene, toluene, ethylbenzene, butyl benzene, amylbenzene, hexyl benzene, octyl benzene, biphenyl, terphenyl, diphenylethane, (methylbenzene Base) aromatic hydrocarbon compounds such as diphenylphosphino ethane, dimethyl diphenyl, benzyl toluene；Diphenyl ether, two (methylbenzyl) ethers, two (second Base benzyl) ether, two (butyl benzyl) ethers, two (amyl benzyl) ethers, two (hexyl benzyl) ethers, two (octyl benzyl) ethers, diphenyl Aromatic series ethers made of the aromatic hydrocarbon compounds such as ether, dibenzyl ether are bonded by ehter bond；Diphenyl sulfide, two (methylbenzyls) Thioether, two (Ethylbenzyl) thioethers, two (butyl benzyl) thioethers, two (amyl benzyl) thioethers, two (hexyl benzyl) thioethers, two The aromatic hydrocarbon compounds such as (octyl benzyl) thioether, two (aminomethyl phenyl) thioethers, dibenzyl sulfide are bonded by thioether bond Aromatic thioether class；Methoxybenzene, ethoxybenzene, butyl phenyl ether, dimethoxy benzene, diethoxybenzene, Dibutoxy Benzene etc. Compound made of hydrocarbon compound and aromatic hydrocarbon compound are bonded by ehter bond；Chloromethanes, chloroethanes, chloropentane, chloro-octane, Bromomethane, bromoethane, bromo pentane silane, bromooctane, dichloroethanes, dichloropentane, two chloro-octanes, Bromofume, dibromo pentane, dibromo The halide such as octane, chlorobenzene, bromobenzene, dichloro-benzenes, dibromobenzene；Acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), diisobutyl ketone, The ketones such as cyclohexanone；The amides such as n-methyl-2-pyrrolidone, DMAC N,N' dimethyl acetamide, N,N-dimethylformamide；Diformazan The sulfoxide types such as base sulfoxide；Water.

Reaction temperature is not particularly limited, can be carried out in 0 DEG C~300 DEG C of range.About reaction time, Ke Yishe The fixed arbitrary reaction time, such as can use the remaining quantity of infrared spectrometer tracking isothiocyanate group, it is desired reaching Remaining quantity after stop reaction.

In general, hydroxyl and reacting for isothiocyanate group are slow, thus catalyst can be used.Catalyst is Louis Acid and generate lewis acidic transistion metal compound, organo-tin compound, copper race metal, zinc, iron group metal compound.Make For the concrete example of catalyst, AlX can be enumerated₃、TiX₃、TiX₄、VOX₃、VX₅、ZnX₂、FeX₃、SnX₄(herein, X is halogen, second Acyloxy, alkoxy, aryloxy group) represented by lewis acid and generate lewis acidic transistion metal compound；(CH₃)₃SnOCOCH₃、(C₂H₅)SnOCOC₆H₅、Bu₃SnOCOCH₃、Ph₃SnOCOCH₃、Bu₂Sn(OCOCH₃)₂、Bu₂Sn(OCOC₁₁H₂₃)₂、 Ph₃SnOCH₃、(C₂H₅)₃SnOPh、Bu₂Sn(OCH₃)₂、Bu₂Sn(OC₂H₅)₂、Bu₂Sn(OPh)₂、Ph₂Sn(CH₃)₂、(C₂H₅)₃SnOH、PhSnOH、Bu₂SnO、(C₈H₁₇)₂SnO、Bu₂SnCl₂, organo-tin compound represented by BuSnO (OH) etc.；CuCl, CuCl₂、CuBr、CuBr₂、CuI、CuI₂、Cu(OAc)₂、Cu(acac)₂, olefin acid copper, Bu₂Cu、(CH₃O)₂Cu、AgNO₃、 AgBr, silver picrate, AgC₆H₆ClO₄The compound of Deng Tong race metal；Zn(acac)₂Equal zinc compounds；Fe(C₁₀H₈)(CO)₅、Fe (CO)₅、Fe(C₄H₆)(CO)₃, Co (trimethylbenzene)₂(PEt₂Ph₂)、CoC₅F₅(CO)₇, the compound of iron group metals such as ferrocene etc. (Bu indicates that butyl, Ph indicate that phenyl, acac indicate acetylacetone chelate ligand.).

[with reacting for the compound with amino]

Represented by the reacting by following formula (101) of compound with amino and isothiocyanates.

(in formula, R⁴¹、R⁴²For group defined in above-mentioned formula (100).)

Reaction can be implemented in the presence of solvent, can also implement in the absence of solvent.About in the presence of solvent into The solvent used when row is inert solvent preferably for amino and isothiocyanate group；Although and isothiocyanate group Reaction but the extremely slow solvent of speed for goal response.As preferred solvent, can enumerate pentane, hexane, heptane, The hydrocarbon compounds such as octane, nonane, decane, dodecane, the tetradecane, pentadecane, hexadecane, octadecane, nonadecane；Ether, tetrahydro Furans, Octyl Ether, nonyl ethers, decyl ethers, lauryl ether, myristyl ether, pentadecyl ether, cetyl ether, octadecane Ethers made of the hydrocarbon compounds such as base ether, tetraethyleneglycol dimethyl ether are bonded by ehter bond；Dimethyl sulphide, diethyl thioether, dibutyl Thioether, dihexyl thioether, octyl thioether, nonyl thioether, decyl thioether, dodecyl thioether, myristyl thioether, pentadecyl Thioether made of the hydrocarbon compounds such as thioether, cetyl thioether, octadecyl thioether, nonadecyl thioether are bonded by thioether bond Class；Benzene, toluene, ethylbenzene, butyl benzene, amylbenzene, hexyl benzene, octyl benzene, biphenyl, terphenyl, diphenylethane, (aminomethyl phenyl) The aromatic hydrocarbon compounds such as diphenylphosphino ethane, dimethyl diphenyl, benzyl toluene；Diphenyl ether, two (methylbenzyl) ethers, two (ethyls Benzyl) ether, two (butyl benzyl) ethers, two (amyl benzyl) ethers, two (hexyl benzyl) ethers, two (octyl benzyl) ethers, diphenyl ether, Aromatic series ethers made of the aromatic hydrocarbon compounds such as dibenzyl ether are bonded by ehter bond；Diphenyl sulfide, two (methylbenzyl) sulphur It is ether, two (Ethylbenzyl) thioethers, two (butyl benzyl) thioethers, two (amyl benzyl) thioethers, two (hexyl benzyl) thioethers, two (pungent Base benzyl) aromatic hydrocarbon compounds such as thioether, two (aminomethyl phenyl) thioethers, dibenzyl sulfide be bonded by thioether bond made of virtue Fragrant race's thioether class；The hydrocarbonylations such as methoxybenzene, ethoxybenzene, butyl phenyl ether, dimethoxy benzene, diethoxybenzene, Dibutoxy Benzene Compound made of conjunction object and aromatic hydrocarbon compound are bonded by ehter bond；Chloromethanes, chloroethanes, chloropentane, chloro-octane, bromine first Alkane, bromoethane, bromo pentane silane, bromooctane, dichloroethanes, dichloropentane, two chloro-octanes, Bromofume, dibromo pentane, dibromo are pungent The halide such as alkane, chlorobenzene, bromobenzene, dichloro-benzenes, dibromobenzene；Water.

Reaction temperature is not particularly limited, can be carried out in -50 DEG C~250 DEG C of range.It, can be with about the reaction time The arbitrary reaction time is set, such as can use the remaining quantity of infrared spectrometer tracking isothiocyanate group, the phase reaching Stop reaction after the remaining quantity of prestige.

In general, amino and reacting for isothiocyanate group are fast, because without using catalyst, but also do not negate to make With itself.As catalyst, the catalyst enumerated in above-mentioned [with reacting for the compound with hydroxyl] can be used.

[with reacting for the compound with hydrazide group, amino urea groups or sulfo-amino urea groups]

Compound with hydrazide group, amino urea groups or sulfo-amino urea groups is reacted because used in isothiocyanates Various reactions can occur for the difference of compound, for example, reaction represented by following formula (102).

(in formula, R⁴¹、R⁴²For group defined in above-mentioned formula (100),

Y expression-NH- base or CH₂Base,

Z indicates oxygen atom or sulphur atom.)

Compound with hydrazide group, amino urea groups or sulfo-amino urea groups can be in solvent with reacting for isothiocyanates In the presence of implement, can also implement in the absence of solvent.About the solvent used when carrying out in the presence of solvent, in addition to upper It states outside the solvent enumerated in [with reacting for the compound with hydroxyl], the alcohol such as methanol, ethyl alcohol, propyl alcohol, butanol can also be used Class；Methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methoxy butyl acetate, cellosolve acetate, pentyl acetate, cream The esters such as sour methyl esters, ethyl lactate, butyl lactate.

Reaction in the presence of a catalyst, in the absence of carry out.Using catalyst, it can be used The catalyst enumerated in above-mentioned [with reacting for the compound with hydroxyl].

In the case that compound with hydrazide group or amino urea groups is reacted with isothiocyanates, further preferably further progress Heat treatment.By the heat treatment, can play sometimes improve the rigidity of resin combination, hardness, processability, impact resistance, The effect of the mechanical properties such as flexural fatigue.The principle for playing this effect is still not clear, the present inventor speculate may be by In: pass through heat treatment, such as bonding reaction according to represented by following formula (103) or formula (104) on the right of above-mentioned formula (102) And ring structure is formed in strand.

(in formula, R⁴¹、R⁴², Y, Z be above-mentioned formula (102) defined in group.)

One of preferred embodiment of resin of present embodiment is represented by being selected from 2 or more by following formula (6)~(8) Divalent group composition group at least one kind of structural unit resin.

(in formula, Y¹It indicates organic group, can be-NH- base.)

Y¹Preferably carbon atom number be 1~12 aliphatic group or carbon atom number be 6~12 aromatic group. As carbon atom number be 1~12 aliphatic group, can enumerate by methane, ethane, propane, butane, pentane, hexane, octane, Divalent group derived from the hydrocarbon compounds such as decane；By hexamethylene, cyclooctane, cyclodecane, hexahydrotoluene, ethyl cyclohexane, butyl Hexamethylene, dimethyl cyclohexane etc. have divalent group derived from the compound of cyclic hydrocarbon group；And by benzene, toluene, ethylbenzene, fourth Divalent group derived from the aromatic hydrocarbon compounds such as benzene, own benzene.

There is the resin of several modes the group represented by being selected from by above-mentioned formula (6)~(8) to form in main chain backbone At least one kind of group in group.For example, resin has structural unit represented by following formula (105)~(108).

(in formula, R⁴³Indicate organic group,

2 or more R⁴³It can be the same or different,

J indicates divalent group represented by above-mentioned formula (6), (7) or (8), 2 or more R in same molecule⁴³It can be with J It is identical to can also be different.)

Above-mentioned R⁴³Preferably carbon atom number be 2~25 aliphatic group, carbon atom number be 7~25 with aromatic series Close the aliphatic group that object replaces or the aromatic group that carbon atom number is 8~25.As R⁴³Concrete example, can enumerate from second Alkane, propane, butane, pentane, hexane, octane, decane, dodecane, octadecane, hexamethylene, cyclooctane, dimethyl cyclohexane, two Ethyl cyclohexane, trimethyl-cyclohexane, trimethylethyl hexamethylene, dicyclohexyl ethane, ethylbenzene, diethylbenzene, diphenylethane, Tetramethyl diphenylethane, ethyl alcohol, propyl alcohol, butanol, amylalcohol, hexanol, octanol, decyl alcohol, dodecanol, octadecanol, cyclohexanol, Lotka-Volterra circle system, dimethyl cyclohexanol, diethyl cyclohexanol, cyclonol, trimethylethyl cyclohexanol, dicyclohexyl ethyl alcohol etc. The middle residue removed after 3 hydrogen atoms.

Resin represented by the resin combination of present embodiment further preferably following formula (109).

(in formula, K¹~K^cAt least one kind of group in the group being made of above-mentioned formula (6)~(8) is each independently represented,

L¹~L^cThe group in the group for selecting free style (6)~(8) to form can be contained or not contain by each independently representing Organic group, c indicate 1 or more integer,

M¹And M²The organic group that can contain or not contain isothiocyanate group is each independently represented,

w_cIndicate 1 or more integer.)

In above-mentioned formula (109), w_cIndicate K^c-L^cRepetitive unit quantity.For example, by K¹-L¹And K²-L²This 2 kinds of weights In the case where the resin that multiple unit is constituted, represented by above-mentioned formula (109) is by following formula (110).

At least one of the group that group represented by containing being selected from 2 or more by above-mentioned formula (6)~(8) is formed The manufacturing method of the resin combination of the resin of structural unit is not particularly limited, for example, can be by with hydrazide group, amino The compound of urea groups or sulfo-amino urea groups is manufactured with reacting for isothiocyanates.

Compound with hydrazide group, amino urea groups or sulfo-amino urea groups can be in solvent with reacting for isothiocyanates In the presence of implement, can also implement in the absence of solvent.About the solvent used when carrying out in the presence of solvent, in addition to upper It states other than the solvent enumerated in [with reacting for the compound with hydroxyl], methanol, ethyl alcohol, propyl alcohol, butanol etc. can also be used Alcohols；Methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methoxy butyl acetate, cellosolve acetate, pentyl acetate, The esters such as methyl lactate, ethyl lactate, butyl lactate.

The reaction unit for implementing to use when reaction is not particularly limited, well known reactor can be used.As reaction Device, such as can be by stirred tank, adding pressure type stirred tank, decompression type stirred tank, tower reactor, destilling tower, packed column, film The appropriately combined use of the conventionally known reactor such as distiller.Material to reactor is it is not also specifically limited, can be used public affairs The material known.As the material of reactor, it is Ni-based resistance to that glass system, stainless steel, carbon steel system, haas troy can be used for example Erosion heat-resisting alloy system imposes the material of glass lining to substrate or has carried out the material of Teflon (registered trademark) coating. The cost of SUS304, SUS316, SUS316L etc. it is low it is preferable to use.It as needed, can be with additional flow meter, thermometer etc. Process unit well known to instrument and meter, reboiler, pump, condenser etc., heating can use method well known to steam, heater etc. It carries out, method well known to natural cooling, cooling water, refrigerating medium etc. also can be used in cooling.It can also additional process as needed.

It can manufacture by such method containing comprising selected from being made of the group represented by above-mentioned formula (6)~(8) The resin combination of at least one of the group modification of the resin of structural unit, but according to the difference of reaction condition, also can sometimes It is unable to get target resin.In this case, by further implementing heat treatment as shown below, target can also be produced Resin.

Heat treatment is preferably carried out in 100 DEG C~300 DEG C of range, the range more preferably at 150 DEG C~250 DEG C.Heating Processing can carry out under atmosphere, can also carry out, preferably implement under inert gas atmosphere under inert gas atmosphere.Herein Described inert gas refers to the gases such as nitrogen, helium, argon, neon.In addition, pressure can be pressurization, decompression or atmospheric pressure.To adding The time of heat treatment is not particularly limited, and can be carried out with 1 minute~500 hours ranges, infrared spectroscopy can be used for example Meter tracks the production quantity of group represented by above-mentioned formula (6)~(8), stops heating after reaching desired amount.

In above-mentioned manufacturing method, it is believed that generate base represented by above-mentioned formula (6)~(8) by various reaction paths Group, such as speculate and generate the reaction based on following formula (111), then generate the compound on the right in following formula (111) The reaction of ring structure is formed by following formula (112) or formula (113).

(in formula, R⁴¹And R⁴²For group defined in above-mentioned formula (100),

Y expression-NH- base or organic group,

Z indicates oxygen atom or sulphur atom.)

The resin combination of the modification of present embodiment can be used alone, it is also preferred that being mixed with other resins.Institute Other resins of mixing can be any resin, and well known various resins can be used.

The resin combination of the modification of present embodiment can be used in well known various uses, wherein selected from by gold The purposes as class coating material that at least one of the group of category, glass and plastics composition material surface is formed is suitable.Separately Outside, the resin combination of present embodiment is formed by the reaction of hydrostable functional group, thus is also preferably used for water system Coating.

The resin combination of the modification of present embodiment contains sulphur atom in strand, thus closely sealed with metal surface Property improvement becomes larger.Therefore, resin combination can be suitably used for being coated in the pre-coated metal comprising Rustproof Steel Plate, automobile For assigning aesthetics, weatherability, acid resistance, rust-preventing characteristic, chipping resistance, adaptation etc. in.

" oxazolidine thione "

Preferred 2nd resin is the resin comprising strand represented by following formula (10) in present embodiment.

(in formula, P¹Indicate aliphatic group and/or aromatic group, Q¹It indicates selected from by following formula (11), (12), (13) Or the structural unit of one or more of group of the composition of divalent group represented by (14), 2 or more P¹And Q¹Can it is identical can also With difference, n indicates 2 or more integer.)

In formula, R¹Indicate aliphatic group or aromatic group, X²And Y²Oxygen atom or sulphur atom are each independently represented, 2 or more R in same molecule¹、X²And Y²It can be the same or different respectively.One Q¹In X²And Y²In 1 with Upper is sulphur atom.In other words, a Q1 includes 1 or more sulphur atom.

, it is surprising that constitute structure represented by above-mentioned formula (11)~(14) of the resin in adaptation, particularly It is excellent with the adaptation aspect of metal surface.The principle for playing this effect is still not clear, but the present inventor's supposition may be Because the sulphur atom or oxygen atom that include in the bonding play the effect for improving adaptation.

The content for facilitating the key of heat-resisting sex expression is also related with above-mentioned number-average molecular weight Mn.By the number-average molecular weight of resin Divided by the quantity n for constituting nitrogen-carbon-sulfide linkage sulphur atom and constituting nitrogen-carbon-oxygen bond oxygen atom for including in every 1 molecule¹And it obtains Value (the Mn/n arrived¹) it is preferably 300 or less, more preferably 200 or less, further preferably 150 or less.As described above, this reality The resin combination for applying mode can also have effect in terms of the adaptation with metal, examine in terms of showing this effect Consider, it is also preferred that having more above-mentioned key in every 1 molecule resin.On the other hand, when resin has excessive above-mentioned key, especially Resin has above-mentioned formula (6)~(8), (11)~(14), (41), (42), (45), structural unit represented by (46) or (47) When, the flexibility as one of film performance can be also damaged sometimes.From the aspect of this, Mn/n¹Preferably 50 or more, more excellent It is selected as 70 or more.n¹Such as can calculate as follows: for example by infrared absorption spectrum or¹H-NMR etc. finds out per unit weight The quantity X of the key of (1g) resin¹(unit mol/g), according to formula: n¹=MnX¹It is calculated by above-mentioned number-average molecular weight (Mn). In the case that resin includes nitrogen-both carbon-sulfide linkage and nitrogen-carbon-oxygen bond, n¹Be constitute each key sulphur atom and oxygen atom it is total Number.

R in above-mentioned formula (11)~(14)¹For aliphatic group or aromatic group.Alkyl has aliphatic group, virtue At least one or more in fragrant race's group can also have oxygen atom, nitrogen-atoms etc. other than carbon atom.Aliphatic group is preferred The aliphatic group that carbon atom number is 1~22, the aliphatic group that more preferable carbon atom number is 1~18.Aromatic group is preferred The aromatic group that carbon atom number is 6~22, the aromatic group that more preferable carbon atom number is 6~15.Further preferably carbon atom number For 1~5 aliphatic group be bonded with the aromatic group that carbon atom number is 6~15 made of carbon atom number be 7~20 base Group.

R¹Concrete example can enumerate methylene, dimethylene, trimethylene, tetramethylene, pentamethylene, six methylenes The straight-chain alkyls such as base, eight methylene；Pentamethylene, hexamethylene, cycloheptane, cyclooctane, bis- (cyclohexyl) alkanes etc. are unsubstituted The group in ester ring type hydrocarbon source；Methyl cyclopentane, ethyl cyclopentane, hexahydrotoluene (Isomers), ethyl cyclohexane are (different Structure body), propyl cyclohexane (Isomers), butyl cyclohexane (Isomers), pentylcyclohexane (Isomers), hexyl hexamethylene The group in the alkyl substituted cyclohexane such as alkane (Isomers) source；Dimethyl cyclohexane (Isomers), diethyl cyclohexane are (each Isomers), the group in the dialkyl group substituted cyclohexane source such as dibutyl hexamethylene (Isomers)；1,5,5- 3-methyl cyclohexanol Alkane, 1,5,5- triethyl group hexamethylene, 1,5,5- tripropyl hexamethylene (Isomers), 1,5,5- tributyl hexamethylene (each isomery Body) etc. trialkyls substituted cyclohexane source group；The monoalkyls substituted benzene such as toluene, ethylbenzene, propyl benzene；Dimethylbenzene, diethylbenzene, two Propylbenzene etc. is dialkyl substituted；The group etc. in the aromatic hydrocarbons such as diphenyl alkane, benzene source.

Among these, preferably hexane, benzene, diphenyl methane, toluene, hexamethylene, dimethylbenzene, hexahydrotoluene, different Fo Er Ketone or the group in dicyclohexyl methyl hydride source." group in source " indicates the structure after removing 2 hydrogen atoms in the compound Group.

Alternatively, R¹Preferably carbon atom number be 1~25 aliphatic group, carbon atom number be 6~25 aromatic group. R¹The group of loop coil atom is not contained preferably.R¹Concrete example be from methane, ethane, propane, butane, pentane, hexane, octane, Decane, dodecane, octadecane, hexamethylene, cyclooctane, dimethyl cyclohexane, diethyl cyclohexane, trimethyl-cyclohexane, front three Base ethyl cyclohexane, dicyclohexyl methyl hydride, tetramethyl dicyclohexyl methyl hydride, benzene,toluene,xylene, ethylbenzene, diethylbenzene, hexichol The residue after 2 hydrogen atoms is removed in methylmethane, tetramethyl diphenyl methane etc..There are in the case where isomers, also including should Isomers.

Among these, R¹Preferably divalent group represented by following formula (301)~(306).

(in formula, i indicates 1~12 integer, can be 1~10.)

In above-mentioned formula (10), P¹For aliphatic group and/or aromatic group.P¹Other than with carbon atom, can also have There are oxygen atom, nitrogen-atoms etc..

P in above-mentioned formula (10)¹It include more preferably ehter bond or ester bond, further preferably represented by following formula (114) Group.

(in formula, R⁴³Indicate aliphatic group or aromatic group,

b²Indicate 1~3 integer.2 or more R in same molecule⁴³And b²It can be the same or different respectively.)

In above-mentioned formula (114), R⁴³For aliphatic group or aromatic group.R⁴³Other than with carbon atom, can also have There are oxygen atom, nitrogen-atoms etc..Aliphatic group can be ring type, or non-ring type.The preferred carbon atom number of aliphatic group For 1~22 aliphatic group, the aliphatic group that more preferable carbon atom number is 1~18.The preferred carbon atom number of aromatic group For 6~22 aromatic group, the aromatic group that more preferable carbon atom number is 6~15.Further preferably have carbon atom number be 1~ The group that the carbon atom number for the aromatic group that 5 aliphatic group and carbon atom number bonded thereto are 6~15 is 7~20.

As the R in above-mentioned formula (114)⁴³Preferred specific structure, base represented by following formula (115) can be enumerated Group.

(in formula, R⁴⁴Indicate a kind in the group being made of hydrogen atom, chlorine atom, bromine atom, fluorine atom and methyl with On group,

R⁴⁵Indicate the base in the group being made of the group represented by following formula (116), (117), (118) or (119) Group,

2 or more R⁴⁴It can be the same or different.)

More specifically, the P in above-mentioned formula (10)¹Preferably group represented by following formula (201)~(204).

In above-mentioned formula (11)~(14), X²And Y²Each independently represent oxygen atom or sulphur atom, the X in a unit²With Y²It is not simultaneously oxygen atom.That is, the X in a unit²And Y²At least one of be sulphur atom.By the inclusion of sulphur atom, with quilt It the adaptation of convered structure, particularly is improved with the adaptation of metal surface.

The structure of end is not shown in structure represented by above-mentioned formula (10), but purport of the invention is epoxy in one aspect The improvement of adaptation in resin and modified epoxy etc., as described above, (of the invention as constituting in the compound of the present invention Compound atom) comprising sulphur atom and/or oxygen atom be critically important, it is believed that the difference of end structure may not necessarily generate compared with Big influence.In addition, as described later, compound represented by above-mentioned formula (10) can pass through the compound with terminal epoxy groups With the compound with end isothiocyanate group (- NCS), the compound with end-rings sulfenyl and with terminal isocyanate The compound of base (- NCO) or end-rings sulfenyl and compound combination with end isothiocyanate group are manufactured. The difference of the compound used according to the compound of above-mentioned formula (10) in order to obtain, the structure of end can be epoxy group, ring Sulfenyl, isocyanate group or isothiocyanate group.In addition, as in<manufacturing method>record as, to isocyanate group into Isocyanurate group obtained from row tripolymer (being different thiocyanuric acid ester group in the case where different thiocyanuric acid ester group) is sometimes Also it is contained in the compound of present embodiment.By reacting for alcohol hydroxyl group and the isothiocyanate group in epoxy resin (aftermentioned) N- substitution-the O- in source replaces thiocarbamate base, by the thiol base and isocyanate group in episulfide resin (aftermentioned) N- substitution-the S- for reacting source replaces thiocarbamate base, by the thiol base and isothiocyanate group in episulfide resin The dithiocarbamate groups in reaction source is also included sometimes.

The compound (resin) of present embodiment for example by the compound with terminal epoxy groups and can have end The compound of isothiocyanate group (- NCS), the compound with end-rings sulfenyl with terminal isocyanate group (- NCO) The combination of compound or compound with end-rings sulfenyl and the compound with end isothiocyanate group is made It makes.

The compound (resin) of present embodiment preferably (has terminal isocyanate by compound represented by following formula (31) The compound of perester radical, the compound with end isothiocyanate group), (have with compound represented by following formula (20) The compound of terminal epoxy groups, the compound with end-rings sulfenyl) reaction and obtain.

(in formula, R²Indicate aliphatic group or aromatic group,

R¹Indicate aliphatic group or aromatic group, X and Y²Each independently represent oxygen atom or sulphur atom.)

The combination of compound represented by compound represented by formula (31) and formula (20) is the formula (31) of sulphur atom according to X Compound and/or Y²Compound for the formula (20) of sulphur atom includes that a kind or more of mode is selected.

Compound combination represented by compound represented by formula of more than two kinds (31), formula (20) is reacted respectively When, 2 or more R¹And R²It can be the same or different.

In the compound represented by above-mentioned formula (20), the compound (being also denoted as epoxy resin) with terminal epoxy groups is excellent It is selected as compound represented by following formula (120).

(in formula, R²Indicate aliphatic group or aromatic group.)

It as the concrete example of compound represented by formula (120), can enumerate: to bisphenol-A, Bisphenol F, bisphenol-A D, bis-phenol S, bisphenol-A, tetramethyl Bisphenol F, bisphenol-A D, tetramethyl bisphenol S, tetrabromobisphenol A, tetrachlorobisphenol A, tetrafluoro are double The bisphenols such as phenol A carry out bisphenol-type epoxy resin made of glycidyl；(4- hydroxyls bis- to xenol, dihydroxy naphthlene, 9,9- Base phenyl) other dihydric phenols such as fluorenes carry out epoxy resin made of glycidyls；To 1,1,1- tri- (4- hydroxy phenyl) Three phenols such as methane, 4,4- (1- (4- (1- (4- hydroxy phenyl) -1- Methylethyl) phenyl) ethylidene) bis-phenol shrink sweet Epoxy resin made of oil base；To four phenols such as 1,1,2,2 ,-four (4- hydroxy phenyl) ethane progress glycidyl At epoxy resin；To novolaks, cresol novolak, bisphenol A novolac, bromination novolaks, brominated bisphenol A phenolic aldehyde The novolaks class such as varnish carries out the glycidyls ethers such as phenolic resin varnish type epoxy resin made of glycidyl；Hexahydro The glycidyls esters such as the 2-glycidyl base ester of phthalic acid or dimeric dibasic acid.These compounds with terminal epoxy groups It can be used alone, can also be shared two or more.

In compound represented by above-mentioned formula (20), the compound (being also denoted as episulfide resin) with end-rings sulfenyl is preferred For compound represented by following formula (121).

(in formula, R²Indicate aliphatic group or aromatic group.)

As the concrete example of compound represented by formula (121), can enumerate to bisphenol-A, Bisphenol F, bisphenol-A D, bisphenol S, Bisphenol-A, tetramethyl Bisphenol F, bisphenol-A D, tetramethyl bisphenol S, tetrabromobisphenol A, tetrachlorobisphenol A, tetrafluoro bis-phenol The bisphenols such as A carry out bisphenol type episulfide resin made of thio glycidyl；To xenol, dihydroxy naphthlene, the bis- (4- of 9,9- Hydroxy phenyl) other dihydric phenols such as fluorenes carry out episulfide resin made of thio glycidyl；To (the 4- hydroxyl of 1,1,1- tri- Phenyl) three phenols such as methane, 4,4- (1- (4- (1- (4- hydroxy phenyl) -1- Methylethyl) phenyl) ethylidene) bis-phenol carry out sulphur For episulfide resin made of glycidyl；Thio contracting is carried out to four phenols such as 1,1,2,2 ,-four (4- hydroxy phenyl) ethane Episulfide resin made of water glyceryl；To novolaks, cresol novolak, bisphenol A novolac, bromination novolaks, The novolaks classes such as brominated bisphenol A novolaks carry out the sulphur such as phenolic varnish type episulfide resin made of thio glycidyl For glycidyl ethers；The thio glycidyl esters such as the dithioglycidol base ester of hexahydrophthalic acid or dimeric dibasic acid Class.These compounds with end-rings sulfenyl can be used alone, and can also share two or more.

R in formula (31)¹The hydrocarbon in group that alkyl represented by being preferably selected from by following formula (301)~(306) forms Base.

(in formula, i indicates 1~12 integer, can be 1~10.)

In compound represented by above-mentioned formula (31), the compound (isocyanate compound) with terminal isocyanate group Preferably compound represented by following formula (122).

O=C=N-R¹- N=C=O (122)

(in formula, R¹Indicate aliphatic group or aromatic group.)

As the concrete example of compound represented by formula (122), tetramethylene diisocyanate, pentamethylene can be enumerated Diisocyanate, hexamethylene diisocyanate, 2,2,4- trimethyl -1,6- diisocyanate root close hexane, two isocyanide of lysine Bis- (the isocyanatomethyl)-hexamethylenes of acid esters, isophorone diisocyanate, 1,3-, 4,4 '-dicyclohexyl methyl hydride, two isocyanide Acid esters, 4,4 '-methyl diphenylene diisocyanates, toluene di-isocyanate(TDI) (Isomers), naphthalene diisocyanate (each isomery Body) etc..Compound represented by further preferred formula (122) is the aliphatic diisocyanate that carbon atom number is 4~20, carbon original The alicyclic diisocyanate that subnumber is 8~20.Among these, it is easy for what weatherability, heat-resisting yellow modified, industry obtained Property, preferably hexamethylene diisocyanate, isophorone diisocyanate.These isocyanate compounds can be used alone, It can also be shared two or more.

In compound represented by above-mentioned formula (31), compound (the isothiocyanic acid esterification with end isothiocyanate group Close object) it is preferably compound represented by following formula (123).

S=C=N-R¹- N=C=S (123)

(in formula, R¹Indicate aliphatic group or aromatic group.)

As the concrete example of compound represented by formula (123), tetramethylene diisothio-cyanate, five methylenes can be enumerated Base diisothio-cyanate, hexa-methylene diisothio-cyanate, 2,2,4- trimethyl -1,6- diisothiocyanic acid root close hexane, rely ammonia Bis- (isothiocyanato the methyl)-hexamethylenes of sour diisothio-cyanate, isophorone diisothio-cyanate, 1,3-, 4,4 '-two rings Hexyl methane diisothio-cyanate, 4,4 '-diphenyl methane diisothio-cyanates, toluene diisothio-cyanate (Isomers), Naphthalene diisothio-cyanate (Isomers) etc..Compound represented by further preferred formula (123) is that carbon atom number is 4~20 Aliphatic diisocyanate, the alicyclic diisothio-cyanate that carbon atom number is 8~20.These are with end isothiocyanate group Compound can be used alone, can also be shared two or more.

In the following, by taking the reacting of epoxy resin and isothiocyanate compound as an example, to the system of the compound of present embodiment The method of making is described.It is also same method in the case where replacing epoxy resin using episulfide resin, it can be by following the description In epoxy resin replace with episulfide resin, epoxy group is replaced with into epithio base.In addition, being replaced using isocyanate compound different It is also the same in the case where sulfocyanic ester compound, the isothiocyanate compound in following the description can be replaced with into isocyanates Isothiocyanate group is replaced with isocyanate group by compound.

About the dosage of isothiocyanate compound, preferably its isothiocyanate group is relative to epoxy group to reach 20~60 The amount of equivalent % uses.The dosage of isothiocyanate compound is more preferably 25~50 equivalent %, further preferably 30~47 It equivalent %, is still more preferably 30~45 equivalent %.Isocyanate group in isocyanate compound is in addition to anti-with epoxy group It answers and is formed other than ring structure, be also used to form thioxanthamide key with the alcohol hydroxyl group in epoxy resin or based on different 3 dimerization of cyclisation of thiocyanate groups and form different thiocyanuric acid ester ring.

Reaction usually carries out in the presence of a catalyst.As catalyst, it can be cited for example that butoxy lithium, sodium methoxide The mixing of the lewis acids and the lewis bases such as lewis acid and triphenylphosphine oxide such as equal metal alcoholates, lithium chloride, aluminium chloride Chloride, bromide, iodide, the acetic acid esters of object, tetramethyl-ammonium, tetraethyl ammonium, tetrabutylammonium, benzyl tributyl ammonium etc. etc. Quaternary ammonium salt, triethylamine, N, N- dimethyl benzyl amine, 11 carbon -7- alkene of 1,8- diazabicyclo [5.4.0], 1,4- diaza are double Imidazoles such as tertiary amines, 2-ethyl-4-methylimidazole, the 2- phenylimidazoles such as ring [2.2.2] octane etc..These catalyst can be single It solely uses a kind or is used in mixed way two or more.As catalyst, particularly preferred quaternary ammonium salt and tertiary amine.

Range of the dosage of catalyst usually relative to the total weight of epoxy resin in 5ppm~2wt% uses.Catalyst Dosage be preferably 20ppm~0.5wt%.Catalyst can also be diluted in solvent appropriate and use.

The manufacturing method of present embodiment can carry out under solvent-free conditions, can also be in the presence of solvent appropriate It carries out.

, it is preferable to use n,N-Dimethylformamide, N, N- diethylformamide, N- methyl -2- in the case where using solvent The molten fibre of pyrrolidones, dimethyl sulfoxide, dimethyl acetamide, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), dimethylbenzene, toluene, methyl Agent acetic acid esters, tetrahydrofuran etc. are free of the solvent of reactive hydrogen.

Reaction temperature is usually 80 DEG C~300 DEG C.Preferably 100 DEG C~260 DEG C, further preferably 120 DEG C~220 ℃.If reaction temperature is too low, the activity of catalyst is low, it may occur that generates the side reactions such as isocyanurate ring.In addition, reaction temperature The excessively high activity that catalyst can also occur reduces, and side reaction still carries out.

In the manufacture of the compound of present embodiment preferably, epoxy resin is warming up to specific temperature, by being blown into Dry air, nitrogen etc. and strongly remove the moisture in resin, put into isothiocyanate compound and catalyst later.Isothiocyanic acid The investment method of ester compounds and catalyst can be selected suitably, can disposably be put into, can also be put into several times, and Isothiocyanate compound can continuously be put into.At this point, the investment of isothiocyanates and catalyst can carry out simultaneously, it can also To carry out respectively.In the case where continuous investment, making time is preferably 1~10 hour, more preferably 2~5 hours.Investment Time, the production quantity of different thiocyanuric acid ester ring was possible to increase in short-term.

(preferably 22~42 work as 20~45 equivalent % of epoxy group in the compound preferred epoxy of present embodiment Amount %, further preferably 25~40 equivalent %) it is reacted with the isothiocyanate group in isothiocyanate compound, form oxazole Alkane -2- thioketones ring (be thiazoline -2- ketone ring in the reacting of episulfide resin and isocyanate compound, episulfide resin with it is different It is thiazoline thioketones ring in the reaction of sulfocyanic ester compound).

In epoxy group in the epoxy, the ratio of epoxy group relevant to oxazolidine -2- thioketones ring can for example lead to It crosses following methods to find out: the method for measuring Oxd rate by chemical gimmick；Utilize infrared measure and nuclear magnetic resonance optical spectroscopy The gimmick of equal equipment analysis carries out quantitative method.

Oxd rate is the equivalent % for foring the epoxy group of such as oxazolidine -2- thioketones ring relative to the epoxy group of script. Epoxy group utilizes used ring in the case where being substantially not consumed other than forming the reaction of oxazolidine -2- thioketones ring The epoxy resin of the epoxide equivalent (referred to as Ep1) and weight (referred to as Wt1) of oxygen resin, the obtained -2- containing oxazolidine thioketones ring Epoxide equivalent (referred to as Ep2) and weight (referred to as Wt2), Oxd rate can be found out by following formula.

Oxd rate=100- (Wt2 ÷ Ep2) ÷ (Wt1 ÷ Ep1) × 100

The compound (resin) of present embodiment can contain a part for passing through the alcohol hydroxyl group in epoxy resin or complete Thioxanthamide key obtained from the reacting of portion and the isothiocyanate group in isothiocyanate compound.Sulfo-amino Ethyl formate key amount be preferably 0.9 equivalent/kg or less, more preferably 0.01~0.7 equivalent/kg, further preferably 0.05~ 0.6 equivalent/kg is still more preferably 0.1~0.5 equivalent/kg.

The compound (resin) of present embodiment can be carried out containing the isothiocyanate group in isothiocyanate compound Different thiocyanuric acid ester ring made of 3 dimerizations of cyclisation.The content of different thiocyanuric acid ester ring is preferably containing for oxazolidine -2- thioketones ring The 40 equivalent % or less of amount, more preferably 30 equivalent % or less, further preferably 20 equivalent % or less, still more preferably it is 10 equivalent % or less.If different thiocyanuric acid ester ring is excessive, polymerization stability reduces sometimes when manufacturing.

The compound (resin) of present embodiment preferably contains substantially no isocyanate group.

In order to improve mobility, the melt viscosity of the compound (resin) of present embodiment is preferably lower.Specifically, 125 DEG C of melt viscosity is preferably 8000mPas or less.More preferably 6000mPas or less, it is more preferably It 4000mPas or less, is still more preferably 3000mPas or less.

The water-disintegrable chlorine dose of the compound (resin) of present embodiment is not particularly limited, such as is used in Electrical and Electronic In the case where the use of way, preferably 500ppm or less.More preferably 100ppm or less.

When the compound of the present invention (resin) has epoxy group, modifying agent can use to part or all of epoxy group It is modified.

As modifying agent, it is not particularly limited as long as there is the compound with the functional group of epoxy reaction, it can be with Enumerate the phenol such as dimethlbenzene, tert-butyl phenol, nonyl phenol, bisphenol-A, quinhydrones；N-butanol, gathers butyl cellosolve The alcohols such as ethylene glycol monoethyl ether, ethylene glycol, polypropylene glycol；Butylamine, octylame, diethylamine, methylbutylamine, monoethanolamine, diethanol Amine, N- methylethanolamine, triethylamine hydrochloride, N, the dimethyl ketone of N- dimethyl ethanol amine acetate, amino ethyl ethanolamine The amines such as imines；The carboxylic acids such as acetic acid, lactic acid, 2 ethyl hexanoic acid, lauric acid, 12- hydroxy stearic acid, benzoic acid, dimethanol propionic acid Class；Diethyl disulfide acetate mixture sulfides class, γ-mercaptopropyi dimethoxymethylsilane, γ-sulfydryl third Thio-alcohols such as base trimethoxy silane etc..

In addition, for example, it is also possible to amino is converted into ammonium salt etc. with amine modified acetic acid etc. that further uses, into Conversion of the row to ionic group.

[solidification compound]

The compound (resin) of present embodiment can be mixed with curing agent, for preparing solidification compound.

When to solidify form be the solidification for having used epoxy group, as curing agent, it can be cited for example that ethylenediamine, triethylene The aliphatic amines such as five amine, 1,6- hexamethylene diamine, dimer acid modified ethylenediamine, N- ethylamino piperazine；M-phenylene diamine (MPD), to benzene two Amine, 3,3 '-diaminodiphenylsulfones, 4,4 '-diaminodiphenylsulfones, 4,4 '-diaminodiphenyl-methanes, 4,4 '-diamino hexichol The aromatic amines such as base ether；The thio-alcohols such as terminal sulfhydryl group compound of mercaptopropionic acid ester, epoxy resin；Bisphenol-A, Bisphenol F, bis-phenol AD, bisphenol S, bisphenol-A, tetramethyl Bisphenol F, bisphenol-A D, tetramethyl bisphenol S, tetrabromobisphenol A, tetrachlorobisphenol A, tetrafluoro bisphenol-A, xenol, dihydroxy naphthlene, 1,1,1- tri- (4- hydroxy phenyl) methane, 4,4- (1- (4- (1- (4- hydroxy benzenes Base) -1- Methylethyl) phenyl) ethylidene) bis-phenol, novolaks, cresol novolak, bisphenol A novolac, bromination phenolic aldehyde The phenolic resin classes such as varnish, brominated bisphenol A novolaks；Poly- azelaic acid acid anhydride, methyl tetrahydrophthalic anhydride, methyl hexahydro are adjacent The anhydrides such as phthalate anhydride, methylnadic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic acid dianhydride；2- methyl The imidazoles such as imidazoles, 2-ethyl-4-methylimidazole, 2- phenylimidazole；The hydrazines such as adipic dihydrazide；Dimethyl benzyl amine, 1, The tertiary amines such as 11 carbon -7- alkene of 8- diazabicyclo [5.4.0]；Dicyandiamide etc..In addition, these curing agent can be used alone, It can also be shared two or more.

Solidifying form is to have used the crosslinkable groups introduced by the modification of epoxy group or by the secondary of modified generation In the cured situation of hydroxyl, as curing agent, such as melamine resin, polyisocyanate compound, sealing end isocyanide are used Ester compound etc..In addition, these curing agent can be used alone, can also be shared two or more.

As melamine resin, can exemplify hexa methoxy melamine methylol, methyl-butvl melamine, Butylated melamines etc..In addition, these melamine resins can be used alone, can also be shared two or more.

As polyisocyanate compound, can exemplify tetramethylene diisocyanate, pentamethylene diisocyanate, HDI, 2,2,4 (or 2,4,4)-trimethyl -1,6- diisocyanate roots conjunction hexane, lysine diisocyanate, isophorone two are different Bis- (the isocyanatomethyl)-hexamethylenes of cyanate, 1,3-, 4,4 '-dicyclohexyl methyl hydride diisocyanates, tetramethyl xylene Diisocyanate, toluene di-isocyanate(TDI), 4,4 '-methyl diphenylene diisocyanates, 1,5- naphthalene diisocyanate, tolidine Diisocyanate such as diisocyanate, benzene dimethylene diisocyanate, norcamphane diisocyanate and by these diisocyanates Polyisocyanates derived from ester.These polyisocyanates can be used alone, and can also share two or more.

As the polyisocyanates as derived from diisocyanate, including isocyanurate type polyisocyanates, biuret form Polyisocyanates, carbamate types polyisocyanates, allophanic acid ester type polyisocyanates etc..These polyisocyanates chemical combination Object can be used alone, and can also share two or more.

As blocked isocyanate compounds, using by end-capping reagent to above-mentioned diisocyanate and/or polyisocyanates Compound has carried out closed compound.

As end-capping reagent, it can be cited for example that alcohols, phenols, oximes, lactams, active methylene group class etc..These envelopes End agent can be used alone, and can also share two or more.

It can arbitrarily be selected, usually about the dosage of curing agent relative to the total amount of the compound comprising present embodiment For 0.1~90 weight %.The dosage of curing agent is preferably 0.1~50 weight %.

Solidification compound can according to need comprising solvent.As solvent, can according to purpose and purposes from such as benzene, The hydro carbons such as toluene, dimethylbenzene, hexamethylene, mineral essential oil, naphtha；The ketones such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK)； The esters such as ethyl acetate, n-butyl acetate, propylene glycol methyl ether acetate；Methanol, isopropanol, n-butanol, butyl cellosolve, fourth The alcohols such as base carbitol；It is suitable for selecting to use in the groups such as water.These solvents can be used alone, and can also share two or more.

Solidification compound can according to need comprising curing accelerator.As curing accelerator, using such as imidazoles, Metallic catalysts classes such as tertiary amines, phosphine, aminotriazole(ATA) class, tin system, zinc system etc..These curing accelerators can be used alone, It can also share two or more.

In solidification compound, common pigment, filler, addition in the technical field as shown below can be used Agent etc..It can be cited for example that the organic pigments such as quinacridone, azo system, phthalocyanine system, titanium dioxide, metal foil-like pigment, anti- Become rusty the fillers, amine system of being obstructed, benzo such as inorganic pigments, barium sulfate, calcium carbonate, silica, carbon black, talcum, the clays such as pigment The antioxidants such as the ultraviolet absorbing agents such as triazole system, benzophenone series, hindered phenolic, phosphorus system, sulphur system, hydrazides system, silane system, titanium Additives such as coupling agents, levelling agent, rheology control agent, pigment dispersing agent, anticrater agent, the defoaming agents such as system etc..In addition, according to need It wants, the reinforcing materials such as glass fibre, glass cloth, carbon fiber can be contained.

The solidification compound of present embodiment has both excellent adaptation and good mobility, is suitable as powder painting Coating, cement, sealing material, moulding material, composite material, laminated board, the encapsulating materials such as material, electrocoating paint, PCM coating Equal materials.

" resin with different thiocyanuric acid ester structure "

Preferred 3rd resin has structural unit represented by 2 or more following formula (40) in present embodiment.The resin One or more of the group that further there is 1 valence, divalent or trivalent group represented by being selected from by following formula (41)~(47) to form Structural unit.R in structural unit represented by formula (41)~(47)³Formula can be formed with isothiocyanate group Direct Bonding (40) structural unit.N in 1 structural unit represented by formula (41)~(47) not with represented by formula (41)~(47) its N Direct Bonding in its structural unit.

SCN-R³- (40)

(in formula, R³Indicate organic group, R⁴Indicate aliphatic group or aromatic group, X³Indicate that oxygen atom or sulphur are former Son.2 or more R in same molecule³、R⁴And X³It can be the same or different.R³It can be aliphatic group or aromatic series Group.)

In general, constituting substantial whole nitrogen-atoms of the polyisothiocyanates in conjunction at least one carbon atom.That is, each knot Structure unit does not pass through N and is bonded directly with one another.In addition, the R in each structural unit³It can be with isothiocyanate group Direct Bonding, shape Structural unit represented by an accepted way of doing sth (40).For example, be bonded by structural unit represented by formula (41) with isothiocyanate group, it can To form two functionality repetitive units represented by mono-functional's repetitive unit represented by formula (46) or formula (47).Polyisocyanate Thiocyanates can have not with R³The isothiocyanate group of bonding.

To-the X for including in formula (43) and (45)³-R⁴Represented functional group is illustrated.

In the manufacturing method of aftermentioned polyisothiocyanates, there is N represented by formula (43), N '-two to replace two for manufacture N- substitution-O- represented by thio allophanic acid key or formula (45) replaces thiocarbamate base or N- substitution-S- to replace When the polyisothiocyanates of dithiocarbamate groups, hydroxy compounds, thio-alcohol are used.-X³-R⁴Represented functional group It is the group from the hydroxy compounds or thio-alcohol, using hydroxy compounds, X³For oxygen atom, sulphur is being used In the case where alcohols, X³For sulphur atom.

About the R in formula (40)~(47)³, as aliphatic group, preferably carbon atom number be 1~22 fatty group Group, the aliphatic group that more preferable carbon atom number is 1~18.As aromatic group, preferably carbon atom number be 6~22 fragrance Race's group, the aromatic group that more preferable carbon atom number is 6~15.The aliphatic group for being further preferably 1~5 with carbon atom number The group that the carbon atom number for the aromatic group for being 6~15 with the carbon atom number being bonded with the aliphatic group is 7~20.

Among these, R³Preferably divalent group represented by following formula (301)~(306).

(in formula, i indicates 1~12 integer, can be 1~10.)

As R⁴Concrete example, can enumerate methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, Decyl, dodecyl, octadecyl, cyclopenta, cyclohexyl, suberyl, cyclooctyl, methylcyclopentyl, ethylcyclopentyl, methyl Cyclohexyl, ethylcyclohexyl, propylcyclohexyl, butylcyclohexyl, pentylcyclohexyl, hexyl cyclohexyl, Dimethylcyclohexyl, two Ethylcyclohexyl, dibutyl cyclohexyl, phenyl, aminomethyl phenyl, ethylphenyl, propyl phenyl, butyl phenyl, amyl phenyl, oneself Base phenyl, octyl phenyl, nonyl phenyl, cumyl phenyl, 3,5-dimethylphenyl etc..

, it is surprising that the heat resistance for constituting structural unit represented by above-mentioned formula (41)~(47) of the resin is high, Adaptation, particularly excellent adhesion with metal surface.It is still not clear about the principle that can play this effect, the present inventor Supposition may be due to heat resistance can be improved when having 6 stable ring structure, the sulphur atom for including can be played and be mentioned in the bonding The effect of high adhesion.

The resin of present embodiment preferably makes to have nitrogen-carbon-sulfide linkage compound and polyisothiocyanates reaction and obtain The resin arrived.Nitrogen-carbon-sulfide linkage is made of nitrogen-atoms, carbon atom and sulphur atom, these atoms are successively bonded.

In addition, the resin of present embodiment preferably through include by compound represented by following formula (33) polymerize step Resin obtained from rapid method.

SCN-R³-NCS (30)

(in formula, R³It indicates organic group, can be aliphatic group or aromatic group.)

In above-mentioned formula (30), R³It indicates aliphatic group, aromatic group or (is had by the group that their combination is formed The aliphatic group that aromatic group replaces).The compound of formula used in monomer as polymerization (30) can be R³It is different Compound of more than two kinds combination.Other than carbon atom, as R³Aliphatic group and aromatic group can also have There are oxygen atom, nitrogen-atoms etc..As aliphatic group, preferably carbon atom number be 1~22 aliphatic group, more preferable carbon atom The aliphatic group that number is 1~18.The aromatic group that the preferred carbon atom number of aromatic group is 6~22, more preferable carbon atom The aromatic group that number is 6~15.Further preferably with carbon atom number be 1~5 aliphatic group and with the aliphatic group key The group that the carbon atom number for the aromatic group that the carbon atom number of conjunction is 6~15 is 7~20.

As R³Concrete example, methylene, dimethylene, trimethylene, tetramethylene, pentamethylene, six can be enumerated The straight-chain alkyls such as methylene, eight methylene；Pentamethylene, hexamethylene, cycloheptane, cyclooctane, bis- (cyclohexyl) methane etc. are unsubstituted Ester ring type hydrocarbon source group；Methyl cyclopentane, ethyl cyclopentane, hexahydrotoluene (Isomers), ethyl cyclohexane are (each Isomers), propyl cyclohexane (Isomers), butyl cyclohexane (Isomers), pentylcyclohexane (Isomers), hexyl ring The group in the alkyl substituted cyclohexane such as hexane (Isomers) source；Dimethyl cyclohexane (Isomers), diethyl cyclohexane The group in the dialkyl group substituted cyclohexane sources such as (Isomers), dibutyl hexamethylene (Isomers)；1,5,5- front three basic ring Hexane, 1,5,5- triethyl group hexamethylene, 1,5,5- tripropyl hexamethylene (Isomers), 1,5,5- tributyl hexamethylene are (different Structure body) etc. trialkyls substituted cyclohexane source group；The monoalkyls substituted benzene such as toluene, ethylbenzene, propyl benzene；Dimethylbenzene, diethylbenzene, Dipropyl benzene etc. is dialkyl substituted；The group etc. in the aromatic hydrocarbons such as benzene source.

Among these, be preferably selected from by hexane, benzene, diphenyl methane, toluene, hexamethylene, dimethylbenzene, hexahydrotoluene, The group of one or more of the group of isophorone or the group in dicyclohexyl methyl hydride source composition." group in source " indicate from The group of the structure after 2 hydrogen atoms is removed in the compound.

R in above-mentioned formula (30)³More preferably group represented by following formula (301)~(306).

(in formula, i indicates 1~12 integer, can be 1~10.)

As isothiocyanates represented by above-mentioned formula (30), hexa-methylene diisothiocyanic acid may further be preferably enumerated Ester, isophorone diisothio-cyanate, 4,4 '-dicyclohexyl methyl hydride diisothio-cyanates, the different sulphur cyanogen of 4,4 '-diphenyl methane two Acid esters, toluene diisothio-cyanate (Isomers), naphthalene diisothio-cyanate (Isomers) etc..

Then, the manufacturing method of the resin of present embodiment (polyisothiocyanates) is illustrated.

The polyisothiocyanates of present embodiment can for example be obtained and making monomer diisothio-cyanate homopolymerization.Monomer The polymerization of diisothio-cyanate preferably carries out in the presence of the catalyst such as aftermentioned different thiocyanuric acid esterification catalyst.In addition, When by monomer diisothiocyanic acid polyisocyanate polyaddition, hydroxy compounds or thio-alcohol can also be used as auxiliary material, pass through two different sulphur cyanogen Acid esters carries out urethane, allophanic acid to a part of isothiocyanate group with hydroxy compounds or reacting for thio-alcohol Esterification etc., thus obtains polyisothiocyanates.

Monomer diisothio-cyanate refers to compound represented by above-mentioned formula (33).

As hydroxy compounds, can enumerate methanol, ethyl alcohol, propyl alcohol, butanol, amylalcohol, hexanol, enanthol, octanol, decyl alcohol, Dodecanol, cyclopentanol, cyclohexanol, suberol, Lotka-Volterra circle system, methylcyclopentanol, ethyl cyclopentanol, methyl cyclohexanol, ethyl ring Hexanol, cyclohexyl alcohol, butylcyclohexyl alcohol, amyl cyclohexanol, hexyl cyclohexanol, dimethyl cyclohexanol, diethyl cyclohexanol, two Butylcyclohexyl alcohol, phenol, methylphenol, ethyl -phenol, propylphenol, butylphenol, amyl phenol, hexylphenol, octyl benzene Phenol, nonyl phenol, cumyl phenol, xylenol, Methylethyl phenol, methyl-propyl phenol, methyl butyl phenol, methylpent Base phenol, diethyl phenol, ethyl propyl phenol, ethyl-butyl phenol, dipropyl phenol, dicumyl phenol, pseudocuminol, Triethyl group phenol, naphthols etc..Alternatively, it is also possible to use ethylene glycol, 1,2-PD or 1,3-PD, 1,3-BDO, 1, 4- butanediol or 2,3- butanediol, 1,6-HD, neopentyl glycol, neopentyl glycol 3-hydroxypivalic acid ester, 2- ethyl -1,3- oneself two The low molecular weight compounds such as alcohol, trimethylolpropane, glycerol, 1,2,6- hexanetriol and number-average molecular weight about 200~10,000 Polyester polyol, polyether polyol etc..

In the case where using hydroxy compounds, the isothiocyanates of above-mentioned hydroxy compounds and monomer diisothio-cyanate Base/hydroxyl equivalent ratio can be selected from 10~100 or so value according to purpose.Also the same, isothiocyanates when using thio-alcohol Base/sulphur hydroxyl equivalent ratio can be selected from 10~100 or so value according to purpose.

As the different thiocyanuric acid ester for being used to form different thiocyanuric acid ester group represented by above-mentioned formula (41), (46) or (47) Change catalyst, preferably quaternary ammonium salt, more preferably quaternary ammonium hydroxide, quaternary ammonium carboxylic acid, further preferred quaternary ammonium carboxylic acid.

As the concrete example of different thiocyanuric acid esterification catalyst, tetramethylammonium hydroxide, tetraethyl hydroxide can be enumerated The tetra-alkyl ammonium hydroxides such as ammonium, tetrabutylammonium hydroxide；Acetic acid tetramethyl ammonium, acetic acid tetraethyl ammonium salt, tetrabutylphosphoniuacetate acetate ammonium Organic monoacids salt such as salt etc..Also the metal of the alkyl carboxylic acids such as acetic acid, valeric acid, isovaleric acid, caproic acid, octanoic acid, tetradecylic acid can be used Salt etc., from the aspect of it can reduce dosage, preferred organic monoacid salt etc..

Above-mentioned different thiocyanuric acid esterification catalyst uses after can diluting.As diluent, hydroxy compounds can be used. As hydroxy compounds, it can be cited for example that such as methanol, ethyl alcohol, n-butyl alcohol or 2- butanol, 2- methyl-1-propyl alcohol, 1,2- third The alcohol hydroxyl groups chemical combination such as glycol or 1,3- propylene glycol, 1,3 butylene glycol, 1,4- butanediol or 2,3- butanediol, glycerol, cyclohexanol The phenolic hydroxyl group compound such as object, phenol, cresols, dimethlbenzene, pseudocuminol.From the crystallization of thus obtained polyisocyanates Property in terms of set out, preferably 2- butanol, 2- methyl-1-propyl alcohol, 1,3-BDO or 2,3-butanediol etc. have side chain alcohol.Separately Outside, it can also be mixed two or more.Thio-alcohol can be used instead of the hydroxy compounds.

Make above-mentioned monomer diisothio-cyanate individually or be to carry out monomer diisothio-cyanate with hydroxy compounds When the isothiocyanate compound of urethane is reacted in the presence of above-mentioned different thiocyanuric acid esterification catalyst, According to above-mentioned hydroxy compounds dilution after different thiocyanuric acid esterification catalyst concentration be 1~20 mass % condition into Row.Above-mentioned concentration is preferably 1~10 mass %.If concentration is 1 mass % or more, associated with different thiocyanuric acid esterification catalyst The amount of hydroxy compounds will not become excessively, and the physical property of obtained polyisothiocyanates and the film being consequently formed is difficult to drop It is low.If concentration is 20 mass % hereinafter, the co-catalysis effect of associated hydroxy compounds will not reduce, as a result, being difficult to cause Increase, coloring of polyisothiocyanates of the dosage of different thiocyanuric acid esterification catalyst etc..

In addition to different thiocyanuric acid esterification catalyst because in the raw materials such as monomer diisothio-cyanate it is micro containing acid ingredient And except in the case of inactivating, the dosage of different thiocyanuric acid esterification catalyst relative to the weight of monomer diisothio-cyanate be 1ppm~ It 10%, is preferably 10ppm~5%.The amount of catalyst can then give full play to and be esterified as different thiocyanuric acid if 1ppm or more The function of catalyst.The amount of catalyst is if 3% hereinafter, can then cut down for making different thiocyanuric acid esterification catalyst inactivation The additive amount of the reaction terminating agents such as acid phosphatase compound, acid phosphoesterase compound (aftermentioned).

Different thiocyanuric acid esterification 30 DEG C~120 DEG C, preferably 50 DEG C~100 DEG C carry out.The progress of reaction can be with Pass through reaction solution¹H-NMR analyzes to confirm.At the time of reaction reaches desired conversion ratio, by putting into reaction terminating Agent makes catalyst inactivation, to stop reacting.Conversion ratio selected in the range of 10~60% be it is suitable, preferably 10~ 30%.When conversion ratio is low, the lower polyisothiocyanates of viscosity can be obtained, but from the aspect of productivity, is preferably converted Rate is 10% or more.On the other hand, if conversion ratio be 60% hereinafter, if the viscosity of polyisothiocyanates will not become excessively high, because And it is preferred that.

Conversion ratio can be found out by following formula.About above-mentioned conversion ratio,¹In H-NMR spectrum, by the methyl of tetramethylsilane Peak be set as 0ppm, conversion is calculated by the integrated value (B) at the peak of the integrated value (A) and 4.8ppm at the peak of 3.5ppm according to the following formula Rate.

Conversion ratio (%)=B/ (A+B) × 100

As the reaction terminating agent of different thiocyanuric acid esterification, using selected from by acid phosphatase compound and acid phosphatase The compound of one or more of the group of ester compounds composition.

Acid phosphatase compound is inorganic acid, it can be cited for example that phosphoric acid, phosphorous acid, ortho phosphorous acid, diphosphorous acid, secondary phosphorus Acid, pyrophosphoric acid, peroxide phosphoric acid etc..Preferably phosphoric acid.

Acid phosphoesterase compound is the compound with acidic-group and ester group, it can be cited for example that carbon atom number is 2 Dialkyl phosphate, dialkyl group phosphorous acid of~8 monoalkyl phosphoric acid esters, monoalkyl phosphite ester, carbon atom number for 4~16 Ester, didodecyl phosphate, diphenyl phosphate, mono phosphoric acid ester lauryl, phosphoric acid monophenyl, phosphorous acid dilauryl, phosphorous acid hexichol Ester, phosphorous acid list lauryl, phosphorous acid monophenyl etc..It is preferred that monoalkyl phosphoric acid esters or carbon atom that carbon atom number is 3~8 The dialkyl phosphate that number is 6~16, more preferably dioctylphosphoric acid ester or mono-octyl phosphate.

, it is preferable to use acid phosphatase compound among these.The additive amount of acid phosphatase compound is urinated relative to different sulphur cyanogen The stoichiometry of acid esterification catalyst is preferably 1~10 equivalent, more preferably 1~6 equivalent.Additive amount if 1 equivalent more than, Different thiocyanuric acid esterification catalyst can be made sufficiently to inactivate.Additive amount is if 10 equivalents hereinafter, the filtering of generated insoluble matter It will not become difficult, thus preferably.

Using acid phosphatase compound, the different thiocyanuric acid esterification catalyst of inactivation in many cases can Insoluble matter is formed, can be removed by filtration.By with being filtered to remove, so as to make the acid phosphatase in polyisothiocyanates The phosphorus in compound source is reduced to the degree for only detecting denier.

Using acid phosphoesterase compound, acid phosphoric acid ester and the salt with different thiocyanuric acid esterification catalyst It is dissolved in polyisothiocyanates, thus is mixed into the modified polyisocyanate after eliminating monomer diisothio-cyanate sometimes In.

From concentration aspect of the phosphorus in polyisothiocyanates, it is preferable to use acid phosphatase compound.Using acid Property phosphate cpd in the case where, by after adding acid phosphatase compound 90~150 DEG C, preferably 100~120 DEG C keep 30~120 minutes, thus the filtration time cripetura in filter progress, filterability was improved.

After obtaining polyisothiocyanates, acid phosphatase compound, acid phosphoesterase compound can be added, especially may be used To add acid phosphatase compound.

As described above, removing the different sulphur of unreacted monomer two from reaction solution after stopping different thiocyanuric acid esterification Cyanate and solvent, are refined.As refining methd, vacuum distillation, solvent extraction etc. can be enumerated, generally can be used thin Membrane distiller.

The content of monomer diisothio-cyanate in polyisothiocyanates after purification can be set as preferred 1.0 matter Measure % or less, preferred 0.5 mass % or less.The unreacted monomer diisothio-cyanate of recycling can reuse.

Polyisothiocyanates can also be used in mixed way with organic solvent.In this case, preferably not having as organic solvent The functional group reacted with hydroxyl and isocyanate group.As such organic solvent, can be used ester compounds, ketone compound, Aromatic compound etc..

Can also be mixed according to purpose, in polyisothiocyanates promote urethane reaction etc. curing accelerator, The various additives such as pigment, levelling agent, antioxidant, ultraviolet absorbing agent, light stabilizer, plasticizer, surfactant and make With.

Polyisothiocyanates can be in dual liquid type polyurethane coating, sealing material, cement, ink, smears, casting mold material It is effectively sharp in the extensive fields such as material, elastomer, foam, plastic raw materials, fibre finish, single solution curing type polyisothiocyanates With.

Embodiment

In the following, illustrate the present invention based on embodiment, but the scope of the present invention and it is not limited to these examples. It is recorded as long as no special, then " part " or " % " in embodiment and comparative example is weight basis.

[analysis method]

(1)¹H-NMR analysis

About 0.3g sample is weighed, deuterated chloroform (U.S., the manufacture of Aldrich society, 99.8%) about 0.7g is added and as interior Tetramethylsilane (Japan, the Wako Pure Chemical Industries, Ltd.'s manufacture and light level-one) 0.05g of ministerial standard substance is simultaneously uniformly mixed, will Obtained solution analyzes sample as NMR.Using the sample, the JNM-A400FT-NMR manufactured by Japan Electronics (strain) society System is analyzed.

It should be noted that the conversion ratio of isocyanate group when manufacture polyisocyanates is counted using following methods It calculates.

?¹In H-NMR spectrum, the signal of the methyl of tetramethylsilane is set as 0ppm, according to the following formula by coming from monomer two The integrated value of the signal of the integrated value (A) and the 3.8ppm from isocyanurate structure of the signal of the 3.3ppm of isocyanates (B) conversion ratio is calculated.

Conversion ratio (%)=B/ (A+B) × 100

In addition, the conversion ratio of isothiocyanate group when manufacture polyisothiocyanates is calculated using following methods.

?¹In H-NMR spectrum, the signal of the methyl of tetramethylsilane is set as 0ppm, according to the following formula by coming from monomer two The integral of the signal of the integrated value (A) and the 4.8ppm from different thiocyanuric acid ester structure of the signal of the 3.5ppm of isothiocyanates Value (B) calculates conversion ratio.

Conversion ratio (%)=B/ (A+B) × 100

(2) number-average molecular weight

Use Tosoh society manufacture GPC-8020 as measurement device, uses tetrahydrofuran as developing solvent, use Tosoh Society manufactures TSKgel SuperH3000, SuperH2000, SuperH1000 as column, carries out gel osmoticing chromatogram analysis (GPC Analysis).About 10mg sample is dissolved in the tetrahydrofuran of 10mL as measurement sample, injection rate is 10 μ L.By with utilization The elution time of polystyrene known to the molecular weight of differential refraction rate detector observation is compared, and finds out number-average molecular weight.

(3) Evaluation of Heat Tolerance method

Using TG-8120 (manufacture of RIGAKU society), in a nitrogen atmosphere with the item of 10 DEG C sample 10mg, heating rate/min Part carries out thermal weight loss measurement, and the case where 5% weight is reduced will not be confirmed within 300 DEG C and is denoted as A, will be within 300 DEG C really Recognize the case where 5% weight is reduced and is denoted as B.

(4) film evaluation method

The adaptation evaluation of film is following to be carried out.It is cut on the film for being formed in aluminium sheet (long 10cm, width 10cm, thickness 5mm) The notch for opening 1mm square, is impregnated in acetone together with aluminium sheet, and it is whether remaining that film is investigated after 24 hours.Every 1 sample carries out 10 same tests, are denoted as A for the situation of 8 pieces or more film remainings, in addition to this case where be denoted as B.

(5) copper-stripping intensity

Copper-stripping intensity is determined according to JIS C 6481.The good situation of copper-stripping intensity is expressed as A, poor situation It is expressed as B.

[embodiment 1]

Put into adipic dihydrazide and polyisocyanates (DURANATE TPA-100, Asahi Chemical Corp's system Make), make isocyanate group and the equivalent proportion of hydrazide group 1.0, mix butyl acetate, prepares the dispersion that solid component is 10% Liquid.The dispersion liquid is stirred 12 hours at 120 DEG C.A part of reaction solution is acquired, is used¹H-NMR is analyzed, and isocyanide is as a result come from Peak near the 3.3ppm of acid esters disappears.After butyl acetate is distilled off using rotary evaporator, heat resistance has been carried out Evaluation.Evaluation result is listed in table 1.

[embodiment 2]

Hydrazine monohydrate 36g is dissolved in isopropanol 1L, is cooled to 0 DEG C, adds hexa-methylene while stirring Diisothio-cyanate 50g.Solid generated is recycled by filtering, is utilized¹H-NMR is analyzed, result 4,4 '- Hexamethylene bis thiosemicarbazide.

For the 4,4 '-hexamethylene bis thiosemicarbazide and polyisocyanates (DURANATE TPA-100, Asahi Chemical Industry Learn Co., Ltd.'s manufacture), method same as Example 1 is carried out, the evaluation of heat resistance is carried out.Evaluation result is listed in table 1.

[embodiment 3]

Hydrazine monohydrate 36g is dissolved in isopropanol 1L, is cooled to 0 DEG C, adds hexa-methylene while stirring Diisocyanate 50g.Solid generated is recycled by filtering, is utilized¹H-NMR is analyzed, result 4,4 '-six Di-2-ethylhexylphosphine oxide semicarbazides.

For the 4,4 '-hexamethylene bis semicarbazides and polyisocyanates (DURANATE TPA-100, Asahi Chemical Industry's chemistry strain The manufacture of formula commercial firm), method same as Example 1 is carried out, the evaluation of heat resistance is carried out.Evaluation result is listed in table 1.

[embodiment 4]

Hydrazine monohydrate 36g is dissolved in isopropanol 1L, is cooled to 0 DEG C, adds metering system while stirring Sour 2- isocyanates root closes ethyl ester 280g.Solid generated is recycled by filtering, is utilized¹H-NMR is analyzed, knot Fruit is methacrylic acid (2- (Hydrazinecarboxamidederivatives) ethyl ester).

Next, methacrylic acid (2- (Hydrazinecarboxamidederivatives) ethyl ester) 100g is dissolved in toluene 1L, metering system is added Sour methyl esters 80g and azodiisobutyronitrile 0.5g, is heated to 80 DEG C.Reaction solution is acquired after 3 hours, is utilized¹H-NMR has been carried out point Analysis, the double bond for as a result constituting methyl methacrylate disappear.Toluene distillation is removed using rotary evaporator, is obtained with ammonia The polymer of base urea groups.

For the polymer and polyisocyanates (DURANATE TPA-100, Asahi Chemical Corp's manufacture), into Row method same as Example 1, carries out the evaluation of heat resistance.Evaluation result is listed in table 1.

[embodiment 5~8]

Side same as Example 1 is carried out in addition to this using hexamethylene diisocyanate instead of polyisocyanates Method carries out the evaluation of heat resistance.Evaluation result is listed in table 1.

[embodiment 9]

Method same as Example 4 is carried out, methacrylic acid (2- (Hydrazinecarboxamidederivatives) ethyl ester) has been manufactured.For the methyl Acrylic acid (2- (Hydrazinecarboxamidederivatives) ethyl ester) and polyisocyanates (DURANATE TPA-100, Asahi Chemical Corp's system Make), method same as Example 1 is carried out, the evaluation of heat resistance is carried out.Evaluation result is listed in table 1.

[reference example 1]

Hexamethylene glycol is used instead of the adipic dihydrazide of embodiment 1, is carried out in addition to this same as Example 1 Method, carry out the evaluation of heat resistance.Evaluation result is listed in table 1.

[reference example 2]

1,6- hexamethylene diamine is used instead of the adipic dihydrazide of embodiment 1, is carried out in addition to this same as Example 1 Method carries out the evaluation of heat resistance.Evaluation result is listed in table 1.

[reference example 3]

Methacrylic acid (2- hydroxy methacrylate) 100g is dissolved in toluene 1L, methyl methacrylate 80g and idol is added Nitrogen bis-isobutyronitrile 0.5g, is heated to 80 DEG C.Reaction solution is acquired after 3 hours, is utilized¹H-NMR is analyzed, and methyl-prop is as a result constituted The double bond of e pioic acid methyl ester disappears.Toluene distillation is removed using rotary evaporator, obtains the polymer with hydroxyl.For this Polymer and polyisocyanates (DURANATE TPA-100, Asahi Chemical Corp's manufacture), carry out same as Example 1 Method, carry out the evaluation of heat resistance.Evaluation result is listed in table 1.

[reference example 4~6]

Hexamethylene diisocyanate is used instead of the polyisocyanates of comparative example 1, is carried out and embodiment 1 in addition to this Identical method carries out the evaluation of heat resistance.Evaluation result is listed in table 1.

[reference example 7]

Methacrylic acid (2- hydroxyethyl) ester is used instead of the adipic dihydrazide of embodiment 1, is carried out in addition to this Method same as Example 1 carries out the evaluation of heat resistance.Evaluation result is listed in table 1.

[table 1]

The manufacture of [Production Example 1] polyisothiocyanates

Making to be equipped with blender, thermometer, reflux condensing tube, nitrogen and be blown into is nitrogen atmosphere, investment six in 4 mouthfuls of flasks of pipe Reactor temperature is remained 130 DEG C under stiring, addition cyclic trimerization catalysis by methylene diisothio-cyanate 600g Agent tetramethyl ammonium caprylate 1.0g.At the time of the conversion ratio of isothiocyanate group reaches 30%, phosphoric acid is added, stops reaction.It crosses After filtering reaction solution, unreacted hexa-methylene diisothio-cyanate is removed using film distillator.Obtained polyisocyanate sulphur cyanogen The number-average molecular weight of acid esters is 620, and isothiocyanate group average is 3.2.

[embodiment 10]

Put into acrylic polyol (Setalux1903；The manufacture of NUPLEX society, trade name；(the resin base of hydroxyl concentration 4.5% It is quasi-), resin solid content 75%) and Production Example 1 obtained in polyisothiocyanates, make the equivalent of isothiocyanate group and hydroxyl Than being 1.0, the dibutyl tin dilaurate for being 0.5 mass % relative to resin is added, mixes butyl acetate, prepare solid at It is divided into 50% resin combination.The resin combination is applied to aluminium sheet using spreader, resin film thickness is made to reach 40 μm.? It is placed at room temperature for after ten minutes, is kept for 10 hours in 150 DEG C of baking oven, obtain cured coating film.To obtained cured coating film Adaptation is evaluated.Evaluation result is listed in table 2.

[embodiment 11]

Polyisothiocyanates obtained in 4,4 '-dicyclohexylmethane diamine and Production Example 1 is put into, isothiocyanate group is made Be 1.0 with the equivalent proportion of amino, mix butyl acetate, prepare the resin combination that solid component is 50%, in addition to this into Row method same as Example 1.The evaluation result of cured coating film is listed in table 2.

[embodiment 12]

Polyisothiocyanates obtained in adipic dihydrazide and Production Example 1 is put into, isothiocyanate group and hydrazide group are made Equivalent proportion be 1.0, mixed ethanol, prepare solid component be 10% resin combination, except this carries out in addition to this in fact Apply the identical method of example 10.The evaluation result of cured coating film is listed in table 2.

[embodiment 13]

Next, methacrylic acid (2- (Hydrazinecarboxamidederivatives) ethyl ester) 100g is dissolved in toluene 1L, methyl-prop is added E pioic acid methyl ester 80g and azodiisobutyronitrile 0.5g, is heated to 80 DEG C.Reaction solution is acquired after 3 hours, is utilized¹H-NMR is divided Analysis, the double bond for as a result constituting methyl methacrylate disappear.Toluene distillation is removed using rotary evaporator, is obtained with ammonia The polymer of base urea groups.

Polyisothiocyanates obtained in the polymer and Production Example 1 is put into, isothiocyanate group and amino urea groups are made Equivalent proportion is 1.0, mixes butyl acetate, prepares the resin combination that solid component is 25%.Using the resin combination, into Row method same as in Example 10, has carried out the evaluation of cured coating film, has as a result been listed in table 2.

[embodiment 14]

Polyisothiocyanates obtained in 4, the 4 '-hexamethylene bis thiosemicarbazide and Production Example 1 is put into, different sulphur cyanogen is made The equivalent proportion of perester radical and sulfo-amino urea groups is 1.0, mixes butyl acetate, prepares the resin combination that solid component is 25% Object.Using the resin combination, method same as in Example 10 is carried out, carries out the evaluation of cured coating film, is as a result listed in table 2.

[reference example 8~12]

Isocyanurate type polyisocyanates (DURANATE TPA-100 is used instead of polyisothiocyanates；Asahi Chemical Industry Chemical Co., Ltd. manufacture, trade name), it carries out method identical with embodiment 10~14 respectively in addition to this, carries out solidification painting The evaluation of film.As a result it is listed in table 2.

[embodiment 15]

Polyisothiocyanates obtained in methacrylic acid -2- hydroxy methacrylate and Production Example 1 is put into, isothiocyanate group is made Equivalent proportion with hydroxyl is hydroxyl/isothiocyanate group=1.3, and butyl acetate is added, and the resin that solid component is 50% is made Composition.The resin combination is heated with 130 DEG C, continues to be heated to¹Until isothiocyanate group disappears in H-NMR.It connects down Come, the resin combination is applied to aluminium sheet using spreader, resin film thickness is made to reach 40 μm.It is being placed at room temperature for after ten minutes, It is kept for 10 hours in 150 DEG C of baking oven, obtains cured coating film.The adaptation of obtained cured coating film is evaluated.It comments Valence result is listed in table 2.

[reference example 13]

Isocyanurate type polyisocyanates (DURANATE is used instead of polyisothiocyanates obtained in Production Example 1 TPA-100；Asahi Chemical Corp's manufacture, trade name), method identical with embodiment 15 is carried out in addition to this.Solidification Film evaluation result is listed in table 2.

[embodiment 16]

Method identical with embodiment 13 is carried out, manufactures methacrylic acid (2- (Hydrazinecarboxamidederivatives) ethyl ester), next obtains The polymer of methacrylic acid (2- (Hydrazinecarboxamidederivatives) ethyl ester).

The polymer and allyl group isosulfocyanate are put into, the equivalent proportion 1.0 of isothiocyanate group Yu amino urea groups is made, Butyl acetate is mixed, the resin combination that solid component is 25% is prepared.The resin combination is applied to using spreader Aluminium sheet makes resin film thickness reach 40 μm.It is being placed at room temperature for after ten minutes, is being kept for 10 hours, solidified in 150 DEG C of baking oven Film.The adaptation of obtained cured coating film is evaluated.Evaluation result is listed in table 2.

[reference example 14]

Instead of allyl group isosulfocyanate using methacrylic acid 2- isocyanates root close ethyl ester, in addition to this carry out with The identical method of embodiment 16.The evaluation result of cured coating film is listed in table 2.

[table 2]

	Adaptation		Adaptation
				Embodiment 10	A	Reference example 8	B
Embodiment 11	A	Reference example 9	B
				Embodiment 12	A	Reference example 10	B
Embodiment 13	A	Reference example 11	B
				Embodiment 14	A	Reference example 12	B
Embodiment 15	A	Reference example 13	B
				Embodiment 16	A	Reference example 14	B

[embodiment 17]

Tetramethylene diisothio-cyanate is added in the eggplant type flask for having the 2L of water 200g and tetrahydrofuran 800g is added After 60 DEG C are stirred 12 hours ethyl isothiocyanate 7g is further added, to being precipitated in 345g and adipic dihydrazide 384g Solid be filtered recycling.Next, adding in the 2L eggplant type flask for having 2 weight % sodium hydrate aqueous solution 1000g is added Enter above-mentioned solid, carry out stirring for 8 hours at 100 DEG C, the solid being precipitated is recycled with filter paper.Measure recycled solid 's¹H-NMR identifies structure.Solid obtained in embodiment 17 is shown in Fig. 1¹H-NMR spectrum.Supposition obtains Resin represented by following formula (124).Number-average molecular weight is 5900, Mn/n based on above-mentioned definition¹It is 150.It needs to illustrate It is X¹By¹H-NMR measures the feed concentrations of sample and the peak (7.26ppm) of chloroform and the nitrogen-atoms direct key with forming ring The ratio between the integrated value at the peak (2.6ppm) of the methene chain of conjunction is found out.

[embodiment 18]

Making to be equipped with blender, thermometer, reflux condensing tube, nitrogen and be blown into is nitrogen atmosphere, investment six in 4 mouthfuls of flasks of pipe Methylene diisothio-cyanate 100g, remains 100 DEG C for reactor temperature under stiring.Thereafter, addition is used as catalyst Tetramethyl ammonium acetate (5.0 mass % solution of 2- butanol) 2g and stir.The appropriate sampling for carrying out reaction solution,¹H-NMR analysis At the time of the conversion ratio of middle isothiocyanate group reaches 21%, phosphoric acid (85 mass % aqueous solution) 0.28g is added, stops reaction. Thereafter, it is further heated 1 hour at 100 DEG C, is cooled to room temperature, after filtering reacting liquid removes insoluble matter, utilizes thin-film distillation Device removes monomer diisothio-cyanate.Monomer diisothiocyanic acid ester concentration is 0.4 mass %, number-average molecular weight 860.

By obtained polyisothiocyanates¹H-NMR spectrum is shown in Fig. 2.It is confirmed by NMR spectra, polyisocyanate thiocyanic acid Ester includes at least structural unit represented by formula (28).Number-average molecular weight is 1200, Mn/n based on above-mentioned definition¹It is 100.It needs It is noted that X¹By¹It is urinated with forming different sulphur cyanogen at the peak (7.26ppm) of feed concentrations and chloroform that H-NMR measures sample The ratio between the integrated value at the peak (3.8ppm) of the methene chain of the nitrogen-atoms Direct Bonding of acid esters ring is found out.

By obtained polyisothiocyanates and acrylic polyol (Dainippon Ink Chemicals's manufacture, trade name: ACRYDICA- 801) mixed, making isothiocyanate group/hydroxyl ratio (equivalent) is 1.0, and being added respectively relative to coating solid ingredient is 0.5% Dibutyl tin dilaurate, ethyl acetate/toluene/butyl acetate/dimethylbenzene/propylene glycol list as solvent or diluent is added thereto The mixed liquor of methyl ether acetate (weight ratio=30/30/20/15/5).Obtained coating solution is applied to air gun On the copper foil that 35 μm of thickness, being adjusted to dry film thickness is 50 μm, and the copper foil that overlapped thickness is 35 μm above is remaining 120 DEG C baking oven in be sintered 30 minutes after, copper-stripping intensity is evaluated.As a result it is listed in table 3.

[embodiment 19~23]

With formula and condition shown in table 3, polyisothiocyanates has been manufactured using method identical with embodiment 18.It uses Obtained polyisothiocyanates, prepares coating solution similarly to Example 18 in addition to this, carries out to copper-stripping intensity Evaluation.As a result it is listed in table 3.

[table 3]

[comparative example 15]

Hexamethylene diisocyanate, the tetramethyl used as catalyst are used instead of hexa-methylene diisothio-cyanate Guanidine-acetic acid ammonium (5.0 mass % solution of 2- butanol) 0.1g, using phosphoric acid (85 mass % aqueous solution) 12mg, utilize in addition to this with The identical method of embodiment 18 has manufactured polyisocyanates.Number-average molecular weight is 1100.Using obtained polyisocyanates, remove Coating solution is prepared similarly to Example 18 other than this, and copper-stripping intensity is evaluated.As a result it is listed in table 4.

[comparative example 16~20]

With formula and condition shown in table 4, polyisocyanates is manufactured using method identical with embodiment 18, to copper-stripping Intensity is evaluated.As a result it is listed in table 4.

[table 4]

[embodiment 24]

Blender, temperature are installed in the removable flask that addition has 100 parts of bisphenol A type epoxy resin (epoxide equivalent 189) Degree meter, reflux condensing tube, nitrogen are blown into pipe, nitrogen are blown into flask, while being warming up to 150 DEG C under stiring, and 150 DEG C of arrival is subsequent Continuous stirring 30 minutes.Reaction temperature is maintained 150 DEG C, in this state with 2 hours dropwise addition hexa-methylene diisothio-cyanates 18.5 parts and tetrabutylammonium chloride (and the pure medicine of light；Practical Grade) 0.05 part of mixture.It, will be warm after completion of dropwise addition Degree is held in 150 DEG C, is reacted.By¹The result (Fig. 3) of H-NMR analysis it is found that obtained comprising following formula (125) or (126) compound of the oxazolidine -2- thioketones ring represented by.The number-average molecular weight of obtained compound is 2,000, is not found The substance that number-average molecular weight is 20,000 or more.It should be noted that being manufactured about above-mentioned number-average molecular weight using Showa electrician society Shodex A-804, A-803, A-802, A802 as column, carried out gel osmoticing chromatogram analysis.About 10mg sample is dissolved As measurement sample in the tetrahydrofuran of 10mL, injection rate is 10 μ L.By being observed with differential refraction rate detector is utilized The elution time of polystyrene known to molecular weight is compared, and finds out number-average molecular weight.Mn/n based on above-mentioned definition¹For 220.It should be noted that X¹By¹H-NMR measures the feed concentrations of sample and the peak for the toluene being added as internal standard (2.3ppm) and the ratio between the integrated value at the peak (4.8ppm) for the methine for foring ring structure are found out.

Obtained compound, curing agent (dicyandiamide) and curing catalysts (2-methylimidazole) are added, are made obtained Resin combination penetrates into glass cloth, and is dried, and thus obtains the prepreg that resin content is 50 mass %.4 pieces of overlapping should Prepreg is overlapped down the copper foil with a thickness of 35 μm, in 190 DEG C of temperature, pressure 20kg/cm on it²Under conditions of heat pressurization 60 minutes, thus produce laminated board.For the laminated board, copper-stripping intensity is evaluated.As a result it is listed in table 5.

[embodiment 25~29]

Using 5 compound represented of table, it is reacted using with the identical method of embodiment 24, and carried out¹H-NMR points As a result analysis has obtained the compound comprising oxazolidine -2- thioketones ring represented by above-mentioned formula (125) or (126).Using acquired Compound, copper-stripping intensity is evaluated using method identical with embodiment 24.As a result it is listed in table 5.

[table 5]

[embodiment 30~35]

Using 6 compound represented of table, it is reacted using with the identical method of embodiment 24, and carried out¹H-NMR points As a result analysis has obtained the compound comprising thiazoline thioketones ring represented by following formula (127) or (128).Using obtained Compound evaluates copper-stripping intensity using method identical with embodiment 24.As a result it is listed in table 6.

[table 6]

[embodiment 36~41]

Using 7 compound represented of table, it is reacted using with the identical method of embodiment 24, and carried out¹H-NMR points As a result analysis has obtained the compound comprising thiazoline -2- ketone ring represented by following formula (129) or (130).Using obtained Compound evaluates copper-stripping intensity using method identical with embodiment 24.As a result it is listed in table 7.

[table 7]

[embodiment 42~59]

Using 8~10 compound represented of table, it is reacted using with the identical method of embodiment 24, and carried out¹H- NMR analysis, has as a result obtained the compound comprising oxazolidine -2- thioketones ring represented by above-mentioned formula (125) or (126).It uses Obtained compound evaluates copper-stripping intensity using method identical with embodiment 24.As a result be listed in table 8~ 10。

[table 8]

[table 9]

[table 10]

[embodiment 60~62]

Using 11 compound represented of table, it is reacted using with the identical method of embodiment 24, and carried out¹H-NMR As a result analysis has obtained the compound comprising thiazoline -2- ketone ring represented by above-mentioned formula (129) or (130).Using acquired Compound, copper-stripping intensity is evaluated using method identical with embodiment 24.As a result it is listed in table 11.

[table 11]

[comparative example 21~26]

Using 12 compound represented of table, it is reacted using with the identical method of embodiment 24, and carried out¹H-NMR As a result analysis has obtained the compound comprising oxazolidone ring represented by following formula (131) or (132).Using obtained Compound evaluates copper-stripping intensity using method identical with embodiment 24.As a result it is listed in table 12.

[table 12]

Claims

1. a kind of resin is by the compound with following functional groups and selected from by monoisocyanates, polyisocyanates, list Obtained from the reaction of at least one kind of compound in the group of isothiocyanates and polyisothiocyanates composition, the functional group is At least one kind of functional group in the group being made of 1 valence group represented by following formula (1), (2), (3), (4) or (5),

-OH (1) -NH₂ (2)

Wherein, which has a cyclic structure, cyclic structure functional group represented by formula (3), (4) or (5) with The reaction of isocyanate group or isothiocyanate group；As the group for containing the cyclic structure, there are 2 or more to be selected under At least one kind of structural unit in the group of the composition of divalent group represented by formula (7) or (8) is stated,

In formula, Y¹Indicate organic group, 2 or more Y in same molecule¹It is identical or different,

When the number-average molecular weight of the resin is Mn, the structure represented by the formula (7) for including in every 1 molecule resin or (8) The sum of quantity of unit is n₂When, Mn is 500 or more, Mn/n₂It is 50 or more 300 or less.

2. resin as described in claim 1 is by the compound with following functional groups and selected from by single different sulphur Resin obtained from the reaction of at least one kind of compound in cyanate and polyisothiocyanates, the functional group are to select free style (1), at least one kind of functional group in the group of the composition of 1 valence group represented by (2), (3), (4) or (5).

3. resin as claimed in claim 1 or 2, wherein the monoisothiocyanates includes change represented by following formula (30) Object is closed,

R⁵-NCS (30)

In formula, R⁵Indicate that aliphatic group, the carbon atom number with aromatic group substitution that carbon atom number is 1~25 are 7~25 Aliphatic group or carbon atom number be 6~25 aromatic group.

4. a kind of resin, in the group that the divalent group represented by being selected from 2 or more by following formula (7) or (8) forms extremely Few a kind of structural unit,

Wherein, when the number-average molecular weight of the resin is Mn, represented by the formula (7) for including in every 1 molecule resin or (8) it is described The sum of quantity of structural unit is n₂When, Mn is 500 or more, Mn/n₂It is 50 or more 300 or less.

5. resin as claimed in claim 1 or 2, wherein the polyisothiocyanates includes change represented by following formula (32) Object is closed,

In formula, R⁶Indicate that organic group, a indicate 2~1000 integer.

6. resin as claimed in claim 1 or 2, wherein the polyisothiocyanates includes to have 2 or more following formula (33) The polymer of represented repetitive unit,

In formula, R⁷Indicate organic group,

R⁸Indicate organic group or singly-bound,

B indicates 1 or more integer,

G indicates 1 or 2,

2 or more R in same molecule⁷、R⁸, b and g difference it is identical or different.

7. resin as claimed in claim 1 or 2, wherein the polyisothiocyanates includes following compounds, compound tool Have:

Structural unit represented by 2 or more following formula (40)；With

Selected from by 1 valence, divalent or the trivalent group group represented by following formula (41), (42), (43), (44), (45), (46) or (47) At group at least one kind of structural unit,

Nitrogen-atoms and carbon atom bonding in the compound,

SCN-R³- (40)

In formula, R³Indicate organic group, R⁴Indicate aliphatic group or aromatic group, X³Indicate oxygen atom or sulphur atom, it is same 2 or more R in molecule³、R⁴And X³It is identical or different respectively.

8. resin as claimed in claim 1 or 2, wherein the polyisothiocyanates includes compound represented by following formula,

SCN-R³-NCS

In formula, R³Indicate organic group.

9. resin as claimed in claim 7, wherein R³For aliphatic group or aromatic group.

10. resin as claimed in claim 8, wherein R³For aliphatic group or aromatic group.

11. the resin as described in claim 9 or 10, wherein R³For following formula (301), (302), (303), (304), (305) Or group represented by (306),

In formula, i indicates 1~12 integer.

12. a kind of resin combination, it includes the resins described in any one of claim 1~11.

13. a kind of class coating material, the resin combination as described in claim 12 is formed.

14. a kind of aqueous coating contains the resin combination described in claim 12.