CN105358602A - Modified resin and resin composition - Google Patents

Modified resin and resin composition Download PDF

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Publication number
CN105358602A
CN105358602A CN201480038533.7A CN201480038533A CN105358602A CN 105358602 A CN105358602 A CN 105358602A CN 201480038533 A CN201480038533 A CN 201480038533A CN 105358602 A CN105358602 A CN 105358602A
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group
formula
resin
compound
represented
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CN201480038533.7A
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CN105358602B (en
Inventor
篠畑雅亮
小杉裕士
三宅信寿
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Asahi Kasei Corp
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Asahi Kasei Chemicals Corp
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Priority to CN201710872612.3A priority Critical patent/CN107629183B/en
Priority to CN202010115257.7A priority patent/CN111205424B/en
Priority to CN202111368897.XA priority patent/CN113929866B/en
Publication of CN105358602A publication Critical patent/CN105358602A/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3228—Polyamines acyclic
    • C08G18/3231—Hydrazine or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes

Abstract

The present invention discloses a resin having a nitrogen-carbon-sulfur bond. The nitrogen-carbon-sulfur bond is constituted by a nitrogen atom, a carbon atom, and a sulfur atom, bonding in the stated order, and the bond between the carbon atom and sulfur atom and/or the bond between the carbon atom and nitrogen atom is a single bond. When the number average molecular weight of this resin is defined as Mn and the number of sulfur atoms constituting the nitrogen-carbon-sulfur bonds contained per resin molecule is defined as n1, Mn is 500 or higher and Mn/n1 is from 50 to 300 inclusive.

Description

The resin of modification and resin combination
Technical field
The present invention relates to resin and the resin combination of modification.
Background technology
Isocyanic ester is known as the raw material of urethane and polyureas.
Urethane is manufactured by the reaction of isocyanate group and hydroxyl, and its tension stress, wear resistant, oil-proofness excellence, be used in coating, joint compound, trolley part etc.For example, Patent Document 1 discloses a kind of bicomponent polyurethane coating for packing film.
Polyureas is manufactured by isocyanate group and amino reaction, and its thermotolerance, physical strength, chemical proofing are excellent, are used in injection-molded article, film, fiber etc.The joint compound of polyureas is used For example, Patent Document 2 discloses a kind of.
Like this, be coated to the surface of metal, glass, plastics based on the urethane of the reaction of isocyanate group and polyureas as coating or joint compound, give function to its surface, but, for this reason must be fully with the adaptation on surface.
As the method improving adaptation, For example, Patent Document 3 discloses a kind of organic aluminum coated steel by surface of steel plate controls the method for the adaptation of carbamate.In addition, as the ameliorative way of be coated with resin side, comprise the composition of polymkeric substance For example, Patent Document 4 discloses a kind of, this polymkeric substance contains acid modified polyolefin system resin dispersion and element sulphur.
The polyisocyantates composition comprising polyfunctional isocyanate compound (polyisocyanates) is used to the purposes widely such as coating composition.Such polyisocyantates composition is such as sold as single-liquid type or two-pack type polyurethane coating composition.Wherein, two-pack type polyurethane coating composition can form fine and close crosslinked film, and finished appearance is good, thus spoken highly of in the purposes of the weathering resistance of the outward appearance of the such requirement high-quality of the top coat purposes of automobile, information household appliances etc. and excellence, weather resistance.
In the top coat of mobile applications, information household appliances purposes etc., except the outward appearance etc. of high-quality, also require that there is scuff resistance and high rigidity.In addition, for the coating composition for the formation of top coat, wish that there is good extensibility.
As the composition comprising polyisocyanates, such as, propose: containing isocyanurate group and phosphorus concentration is the polyisocyantates composition (patent documentation 5) of 0.1 ~ 20ppm; Containing the coating composition (patent documentation 6, patent documentation 7) of polyisocyanates with allophanate group; Coating composition (patent documentation 8) etc. containing the polyisocyantates composition and polyvalent alcohol with allophanate group, is studied the manufacture method of above-mentioned composition and utilization.
The balancing good of the thermotolerance, chemical proofing etc. of epoxy resin, is thus such as used to as materials such as coating, joint compound, formed material, matrix material, laminated board, sealing materials widely in field.
In recent years, compared with existing resin material, require that there is significantly high performance, the resin material of high reliability.Just in research and utilization various modification gimmick, modification is carried out to existing resin.Wherein, have and make a part for oxide-base and isocyanic ester radical reaction and the modified epoxy of 1-oxa--3-azacycloparaffin-2-ketone structure that obtains receives publicity as taking into account high second-order transition temperature and flexible resin, propose many schemes (such as with reference to patent documentation 9, patent documentation 10, patent documentation 11).
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Application Publication 2012-517489 publication
Patent documentation 2: Japanese Unexamined Patent Application Publication 2010-507689 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2001-219498 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2010-163579 publication
Patent documentation 5: Japanese Patent No. 4201582 publication
Patent documentation 6: Japanese Unexamined Patent Publication 8-188566 publication
Patent documentation 7: Japanese Unexamined Patent Publication 7-304724 publication
Patent documentation 8: No. 2002/32979th, International Publication
Patent documentation 9: Japanese Laid-Open Patent Publication 59-135265 publication
Patent documentation 10: Japanese Laid-Open Patent Publication 61-181820 publication
Patent documentation 11: Japanese Unexamined Patent Publication 5-222160 publication
Summary of the invention
Invent problem to be solved
Be coated to the surface of metal, glass, plastics based on the urethane of the reaction of isocyanate group and polyureas as coating or joint compound, give function to its surface, but require the further improvement of thermotolerance.
Therefore, from an aspect, the object of the present invention is to provide the resin combination of the modification that a kind of thermotolerance is high.
On the other hand, carry out surface-treated method to be as described in Patent Document 3 difficult to be suitable for because of surface shape and Facing material under many circumstances.In addition, when the resin compound that patent documentation 4 is such, sometimes because of resin being separated and making adaptation reduce on the contrary each other, or the function of film self is impaired.
Therefore, from another aspect, the object of the present invention is to provide the resin combination of the modification that a kind of adaptation is high.
In addition, according to the research of the present inventor, there is room for improvement in the polyisocyantates composition recorded in patent documentation 5 ~ 8 in the adaptation with adherend, particularly with in the adaptation of metal.
Further from another aspect, the object of the present invention is to provide a kind of polyisothiocyanates good with the adaptation of adherend and manufacture method thereof.
In addition, according to the research of the present inventor,, with the adaptation of adherend, particularly with in the adaptation of metal there is room for improvement in the difference of modified epoxy because of its purposes with 1-oxa--3-azacycloparaffin-2-ketone structure recorded in patent documentation 9 ~ 11.
Again further from another aspect, problem of the present invention is to provide a kind of modified epoxy good with the adaptation of adherend while the characteristic of the compounds such as retaining ring epoxy resins, episulfide resin; With compounds such as the modification episulfide resins that the adaptation of adherend is good; And the manufacture method of these compounds.
For solving the scheme of problem
The present inventor conducts in-depth research to solve above-mentioned problem, found that, by have in molecule ad hoc structure resin, containing the compound reaction enabling to have particular functional group, the resin of compound that obtains solves above-mentioned problem, this completes the present invention.
That is, the present invention relates to following technical proposals.
[1]
A kind of resin, it is the resin with nitrogen-carbon-sulfide linkage, this nitrogen-carbon-sulfide linkage is made up of nitrogen-atoms, carbon atom and sulphur atom, these atoms are with this order bonding, at least one in the bonding of above-mentioned carbon atom and above-mentioned sulphur atom and the bonding of above-mentioned carbon atom and above-mentioned nitrogen-atoms is singly bound, when the number-average molecular weight of this resin be Mn, the quantity of the sulphur atom of the above-mentioned nitrogen-carbon-sulfide linkage of formation that comprises in every this resin of 1 molecule is n 1time, Mn is more than 500, Mn/n 1be less than more than 50 300, n 1by formula: n 1=X 1mn (X 1represent the quantity of the sulphur atom of the above-mentioned nitrogen-carbon-sulfide linkage of the formation comprised in this resin of every 1g) calculate.
[2]
Resin as described in [1], wherein, 5% thermal weight loss temperature of this resin is more than 300 DEG C.
[3]
A kind of resin, it is obtained by the reaction with at least a kind of compound be selected from the group that is made up of monoisocyanates, polyisocyanates, monoisothiocyanates and polyisothiocyanates of the compound with following functional group, at least a kind of functional group in the group that this functional group forms for the 1 valency group be selected from represented by following formula (1), (2), (3), (4) or (5).
-OH(1)-NH 2(2)
[4]
Resin as described in [3], it is above-claimed cpd by having following functional group and be selected from the resin obtained by the reaction of at least a kind of compound in monoisothiocyanates and polyisothiocyanates or monoisothiocyanates or polyisothiocyanates, and this functional group is for selecting at least a kind of functional group in the group of 1 valency group composition represented by free style (1) ~ (5).
[5]
Resin as described in [3] or [4], wherein, above-mentioned monoisothiocyanates comprises the compound represented by following formula (30) or is this compound.
R 5-NCS(30)
(in formula, R 5represent organic group.R 5can for carbonatoms be 1 ~ 25 aliphatic group, with aromatics replace carbonatoms be 7 ~ 25 aliphatic group or carbonatoms be the aromatic group of 6 ~ 25.)
[6]
As the resin according to any one of [3] ~ [5], wherein, above-mentioned resin has the ring texture of the reaction from the above-mentioned functional group represented by formula (3) ~ (5) and isocyanate group or isothiocyanate group.
[7]
Resin as described in [6], wherein, as the group containing above-mentioned ring texture, there are more than 2 at least a kind of structural unit (group) be selected from the group that the divalent group represented by following formula (6), (7) or (8) forms.
(in formula, Y 1represent organic group, with Y more than 2 in a part 1can be the same or different.Y 1it can be-NH-base.)
[8]
A kind of resin, it has more than 2 at least a kind of structural unit (group) be selected from the group that the divalent group represented by following formula (6), (7) or (8) forms.
(in formula, Y 1represent organic group, with Y more than 2 in a part 1can be the same or different.Y 1it can be-NH-base.)
[9]
Resin as described in [7] or [8], wherein, when the number-average molecular weight of this resin be Mn, the quantity sum of the formula (6) that comprises in every this resin of 1 molecule, said structure unit represented by (7) or (8) is n 2time, Mn is more than 500, Mn/n 2be less than more than 50 300, n 2by formula: n 2=X 2mn (X 2represent comprise in this resin of every 1g formula (6), (7) or the said structure unit represented by (8) quantity sum) calculate.
[10]
A kind of resin, it is by having the nitrogen-compound of carbon-sulfide linkage with the reaction of polyisothiocyanates obtains, and this nitrogen-carbon-sulfide linkage is made up of nitrogen-atoms, carbon atom and sulphur atom, and these atoms are with this sequentially bonding.
[11]
As the resin according to any one of [3] ~ [7] and [10], wherein, above-mentioned polyisothiocyanates comprises the compound represented by following formula (32) or is this compound.
(in formula, R 6represent organic group, a represents the integer of 2 ~ 1000.)
[12]
As the resin according to any one of [3] ~ [7] and [10], wherein, above-mentioned polyisothiocyanates comprises the polymkeric substance of the repeating unit had represented by more than 2 following formula (33) or is this polymkeric substance.
(in formula, R 7represent organic group,
R 8represent organic group or singly-bound,
B represents the integer of more than 1,
G represents 1 or 2,
With R more than 2 in a part 7, R 8, b and g can be the same or different respectively.)
[13]
As the resin according to any one of [3] ~ [7] and [10], wherein, above-mentioned polyisothiocyanates comprises following compound or is this compound, and this compound has: the structural unit represented by following formula (40) of more than 2; With at least a kind of structural unit in the group that 1 valency be selected from represented by following formula (41), (42), (43), (44), (45), (46) or (47), divalent or 3 valency groups (unit) form, the nitrogen-atoms in this compound and carbon atom bonding.
SCN——R 9——(40)
(in formula, R 3represent organic group, R 4represent aliphatic group or aromatic group or aliphatic alkyl or aromatic hydrocarbyl, X 3represent Sauerstoffatom or sulphur atom, with R more than 2 in a part 3, R 4and X 3can be the same or different respectively.)
[14]
As the resin according to any one of [3] ~ [7] and [10], wherein, above-mentioned polyisothiocyanates comprises the compound represented by following formula (33) or is this compound.
SCN-R 3-NCS(33)
(in formula, R 3represent organic group.)
[15]
A kind of resin, the method for the step of the compound polymerization represented by following formula (33) obtains by comprising by it.
SCN-R 3-NCS(33)
(in formula, R 3represent organic group.)
[16]
The manufacture method of the resin [15], it comprises the following steps: in the presence of a catalyst by the above-claimed cpd polymerization represented by formula (33).
[17]
A kind of resin, it has:
The structural unit represented by following formula (40) of more than 2; With
Be selected from least a kind of structural unit in the group that 1 valency represented by following formula (41), (42), (43), (44), (45), (46) or (47), divalent or 3 valency groups (structural unit) form
Nitrogen-atoms (N) in 1 said structure unit represented by formula (41) ~ (47) not with nitrogen-atoms (N) Direct Bonding in other said structure unit represented by formula (41) ~ (47).
R in said structure unit represented by formula (41) ~ (47) 3the said structure unit of formula (40) can be formed with isothiocyanate group Direct Bonding.
SCN——R 3——(40)
(in formula, R 3represent organic group, R 4represent aliphatic group or aromatic group,
X 3represent Sauerstoffatom or sulphur atom,
With R more than 2 in a part 3, R 4and X 3can be the same or different respectively.)
[18]
Resin as described in [13], [14], [15] or [17], wherein, R 3for aliphatic group or aromatic group.
[19]
Resin as described in [18], wherein, R 3for the alkyl represented by following formula (301), (302), (303), (304), (305) or (306).
(in formula, i represents the integer of 1 ~ 12, can be 1 ~ 10.)
[20]
A kind of resin combination, it comprises [1] ~ [15] and [17] ~ [19] according to any one of resin.
[21]
A kind of class coating material, it is formed by the resin combination described in [20] or uses this resin combination to be formed.
[22]
A kind of aqueous coating, the resin combination that it contains described in [20].
[23]
A kind of resin, it comprises the molecular chain represented by following formula (10).
(in formula, P 1represent aliphatic group and/or aromatic group, Q 1represent the structural unit (group) of more than a kind be selected from group that the divalent group represented by following formula (11), (12), (13) or (14) forms, the P of more than 2 1and Q 1can be the same or different, n represents the integer of more than 2.)
(in formula, R 1represent aliphatic group or aromatic group,
X 2and Y 2separately represent Sauerstoffatom or sulphur atom, with R more than 2 in a part 1, X 2and Y 2can be the same or different respectively.A Q 1in X 2and Y 2in more than 1 be sulphur atom.)
[24]
Resin as described in [23], wherein, R 1the residue after removing forms 2 isocyanate group (-NCO) of this polyisocyanates from polyisocyanates or the residue remove 2 isothiocyanate groups (-NCS) forming this polyisothiocyanates from polyisothiocyanates after.
[25]
Resin as described in [23] or [24], it is obtained by the reaction being selected from least a kind of compound in polyisocyanates and polyisothiocyanates and the compound represented by following formula (20).
(in formula, R 2represent aliphatic group or aromatic group,
Y 2represent Sauerstoffatom or sulphur atom.The Y of more than 2 in a unit 2can be the same or different.)
[26]
Resin as described in [25], wherein, at least a kind of above-claimed cpd be selected from polyisocyanates and polyisothiocyanates comprises the compound represented by following formula (31).
XCN——R 1——NCX(31)
(in formula, R 1represent aliphatic group or aromatic group,
X represents Sauerstoffatom or sulphur atom.X and Y in a unit 2in at least one can be sulphur atom.)
[27]
Resin as described in [25] or [26], wherein, R 2for 1 valency group represented by following formula (201), (202), (203) or (204).
[28]
As the resin according to any one of [23] ~ [27], wherein, R 1to be carbonatoms the be aliphatic group of 1 ~ 25, the carbonatoms that replaces with aromatic group (aromatics) be 7 ~ 25 aliphatic group or carbonatoms be the aromatic group of 6 ~ 25.
[29]
As the resin according to any one of [23] ~ [27], wherein, R 1be selected from the alkyl in group that the alkyl represented by following formula (301), (302), (303), (304), (305) or (306) forms.
(in formula, i represents the integer of 1 ~ 12, can be 1 ~ 10.)
[30]
As the resin according to any one of [23] ~ [28], wherein, R 1not containing spiro atom.
[31]
A kind of solidification compound, it comprises [23] ~ [30] according to any one of resin and solidifying agent.
[32]
The manufacture method of the resin [25] or described in [26], it comprises the following steps: in the presence of a catalyst, makes to be selected from least a kind of above-claimed cpd in polyisocyanates and polyisothiocyanates and the above-claimed cpd represented by formula (20) reacts.
The effect of invention
According to the present invention, the resin combination of the modification that a kind of thermotolerance is high can be provided.
According to the present invention, the resin combination of the modification that a kind of adaptation is high can be provided.
According to the present invention, a kind of polyisothiocyanates good with the adaptation of adherend and manufacture method thereof can be provided.
According to the present invention, a kind of modified epoxy good with the adaptation of adherend while the characteristic of the compounds such as retaining ring epoxy resins, episulfide resin can be provided; With compounds such as the modification episulfide resins that the adaptation of adherend is good; And the manufacture method of these compounds.
Accompanying drawing explanation
Fig. 1 is the solid obtained in embodiment 17 1h-NMR spectrum.
Fig. 2 illustrates polyisothiocyanates 1the figure of H-NMR spectrogram.
Fig. 3 is the compound that Bao Han oxazolidine-2-thioketones ring is shown 1the figure of H-NMR spectrogram.
Embodiment
Below, this embodiment (hereinafter referred to " present embodiment ") is described in detail.The invention is not restricted to following embodiment, various distortion can be carried out implement in the scope of its main points.
In this specification sheets, compound name uses the title of the rule recorded in the nomenclature (IUPAC organic chemistry nomenclature) based on IUPAC (International Union of Pure and Applied Chemistry(IUPAC)) defined in many cases." organic " refers to the generalization compound group of the object as nomenclature disclosed in this rule.This object can be the object recorded in the suggestion proposed for 1993.Wherein, " organic " compound as the object of above-mentioned nomenclature also comprises organometallic compound and metal complex.In present embodiment, use " organic " and/or the term such as " organic group " and/or " substituting group ", the compound used in following explanation present embodiment, when without special instruction, they are by not comprising atoms metal and/or semimetallic atomic building.In the present embodiment, as the structure by the atomic building be selected from H (hydrogen atom), C (carbon atom), N (nitrogen-atoms), O (Sauerstoffatom), S (sulphur atom), Cl (chlorine atom), Br (bromine atoms), I (atomic iodine), use " organic compound ", " organic group ", " substituting group ".
The term using " aliphatics " and " aromatic series " so in the following description more.According to the rule of above-mentioned IUPAC, describe organic compound and be classified as fatty compounds and aromatics.Fatty compounds refers to the definition of the group of the fatty compounds of advising according to the IUPAC based on nineteen ninety-five.In this suggestion, fatty compounds is defined as " Acyclicorcyclic; saturatedorunsaturatedcarboncompounds; excludingaromaticcompounds (non-ring type or ring type, saturated or unsaturated carbon compound, except aromatics) ".In addition, the fatty compounds used in description of the present embodiment and aliphatic group contain any one in saturated and unsaturated, chain and ring-type, can by being selected from above-mentioned H (hydrogen atom); C (carbon atom); N (nitrogen-atoms); O (Sauerstoffatom); S (sulphur atom); Si (Siliciumatom); Be selected from the halogen atom in Cl (chlorine atom), Br (bromine atoms) and I (atomic iodine); In atomic building.
Have as " aralkyl " and to be sometimes designated as " aliphatic group with aromatic group replaces ", " aromatic-aliphatic group " or " group that the aliphatic group of bonding aromatic group is formed " with the group of the aromatic group of aliphatic group bonding.This is based on the reactivity in present embodiment, because the relevant character of the reaction of the group such to aralkyl is extremely similar to aliphatic reactivity, instead of aromaticity.And, sometimes the non-aromatic reactive group containing aralkyl, alkyl etc. is designated as " aliphatic group that can replace with aromatic series ", " aliphatic group with aromatic series replaces ", " bonding the aliphatic group of aromatic group " etc., is sometimes included in " aliphatic group ".
When the general formula of the compound used in this specification sheets is described, use the definition of the nomenclature rule specified according to above-mentioned IUPAC, but title, the illustrative compound title of concrete group use trivial name sometimes.Further, in this specification sheets, sometimes record the number of atom, substituent number, number, they all represent integer.
When in this specification sheets, illustrative substituting group, compound have constitutional isomer, only otherwise special declaration, then their constitutional isomer is comprised.
< resin combination >
Resin combination involved by some embodiments contains the resin with nitrogen-carbon-sulfide linkage and/or nitrogen-carbon-oxygen bond.Herein said nitrogen-carbon-sulfide linkage refer to nitrogen-atoms, carbon atom, sulphur atom with this order bonding the structure of state, it can be singly bound that the nitrogen-bond with carbon in this key, carbon-sulfide linkage close, and also can be unsaturated link(age) bonding.Wherein, at least one during nitrogen-bond with carbon and carbon-sulfide linkage closes can be singly bound.The nitrogen-atoms and the sulphur atom that form this key can by the bondings such as other atom, such as carbon atom, nitrogen-atoms, Sauerstoffatom, Siliciumatom.Nitrogen-carbon-oxygen bond defines too.
As the group comprising nitrogen-carbon-sulfide linkage and/or nitrogen-carbon-oxygen bond, the structural unit represented by following formula preferably can be enumerated.
(in formula, R 1the residue after removing forms 2 isocyanate group (-NCO) of this polyisocyanates from polyisocyanates or the residue remove 2 isothiocyanate groups (-NCS) forming this polyisothiocyanates from polyisothiocyanates after
X 2and Y 2represent Sauerstoffatom or sulphur atom independently of one another,
X in a structural unit 2and Y 2in more than 1 be sulphur atom.)
(in formula, R 3and R 4represent aliphatic group or aromatic group independently of one another, the R of more than 2 3and R 4can be the same or different,
X 3represent Sauerstoffatom or sulphur atom.)
Resin combination containing the resin in molecule with this structural unit can play and significantly improve the effect with the adaptation of metal.In addition, because its specific refractory power is high, thus also effective to the improvement of the physical properties of coatings such as glossiness.
As characteristic during formation film, thermotolerance is one of key property.Specifically, can for the resin combination of resin containing 5% thermal weight loss temperature being more than 250 DEG C or more than 300 DEG C.Said 5% thermal weight loss temperature refers to following temperature herein: under the inert gas atmospheres such as nitrogen, helium, argon, when resin is heated in temperature per minute rises the stove of 10 DEG C, the temperature of stove during the moment that the weight confirming 5% relative to the weight resin under room temperature (20 DEG C ~ 30 DEG C) reduces, can be used as the commercially available device of thermogravimetric analyzer to measure usually.
For the resin combination of effect playing thermotolerance, according to its main chain backbone, bonding pattern, molecular weight, contribute to the difference of the content etc. of the key of thermotolerance performance, have various.From the aspect of bonding pattern, among above-mentioned, the resin combination of the resin preferably containing the structural unit had represented by above-mentioned formula (6) ~ (8), (11) ~ (14), (41), (42), (45), (46) or (47).
The number-average molecular weight of resin is preferably more than 500, is more preferably more than 1000, more preferably more than 5000.In general, molecular weight is higher, then have the tendency that thermotolerance is better; On the other hand, when molecular weight is too high, sometimes be disadvantageous from the aspect of treatability (with the Combination, mobility, ductility etc. of other composition) when forming film, thus number-average molecular weight is preferably less than 1,000,000, is more preferably less than 500,000, more preferably less than 200,000.Said number-average molecular weight is the value calculated as follows herein: use that to possess at least 1 exclusion limit molecular weight be that the gel permeation chromatography of the post of more than 1,000 ten thousand measures, utilize the reference materials such as polystyrene, hold-time will be converted into molecular weight, calculate thus.Those skilled in the art easily can obtain number-average molecular weight.Calculate after except the peak from solvent.
The content contributing to the key of thermotolerance performance is also relevant with above-mentioned number-average molecular weight Mn.By the quantity of the number-average molecular weight of resin divided by the sulphur atom of the formation nitrogen-carbon-sulfide linkage comprised in every 1 molecule and the quantity n of the Sauerstoffatom of formation nitrogen-carbon-oxygen bond 1and the value (Mn/n obtained 1) be preferably less than 300, be more preferably less than 200, more preferably less than 150.As mentioned above, the resin combination of present embodiment with the adaptation of metal in also can have effect, from the viewpoint of showing this effect, also preferably there is more above-mentioned key in every 1 molecule resin.On the other hand, when resin has too much above-mentioned key, particularly resin have above-mentioned formula (6) ~ (8), (11) ~ (14), (41), (42), (45), (46) or the structural unit represented by (47) time, the flexibility as one of film performance sometimes also can be impaired.From the viewpoint of this, Mn/n 1be preferably more than 50, be more preferably more than 70.N 1such as can calculate as follows: such as by infrared absorption spectrum or 1h-NMR etc. obtain the quantity X of this key of per unit weight (1g) resin 1(unit mol/g), according to formula: n 1=MnX 1calculated by above-mentioned number-average molecular weight (Mn).When resin comprises nitrogen-carbon-sulfide linkage and nitrogen-carbon-oxygen bond, n 1form the sulphur atom of each key and the sum of Sauerstoffatom.
As mentioned above, the feature of the resin comprised in the resin combination of present embodiment is the key (structural unit) forming molecular chain, is not particularly limited the skeleton structure between each key.Specifically, the skeleton structure of the starting compound used in the manufacture method from the resin combination of following illustrative present embodiment is preferably used.
In such resin, the characteristic of the resin containing the structural unit represented by above-mentioned formula (6) ~ (8), (11) ~ (14), (41), (42), (45), (46) or (47) is good, can preferably use.Below, these resins are described.
<< has the resin >> of heterocycle
The preferred structure > of <
In present embodiment, preferred 1st resin has the resin that more than 2 are selected from least one structural unit in the group that 1 valency group represented by above-mentioned formula (6) ~ (8) forms.Surprisingly, the thermotolerance with the resin of the structural unit represented by above-mentioned formula (6) ~ (8) is high, adaptation, particularly with the excellent adhesion of metallic surface.The principle that can play this effect is not yet clear and definite, but the present inventor's supposition may be the ring structure owing to having conjugated system contributes to thermotolerance, and the thiol (-SH base) that the sulphur atom comprised in this structural unit, the particularly structural unit of above-mentioned formula (6) have can play the effect improving adaptation.From the viewpoint of this, preferably comprise the resin of the structural unit represented by above-mentioned formula (6) and/or the structural unit represented by above-mentioned formula (7).
Like this, the feature of the resin of present embodiment is the bonding pattern comprised in its molecule, and be not particularly limited the skeleton structure beyond this bonding, preferred mode is as follows.
The number-average molecular weight of resin is preferably more than 500, is more preferably more than 1000, more preferably more than 5000.In general, molecular weight is higher, then have the tendency that thermotolerance is better; On the other hand, when molecular weight is too high, sometimes be disadvantageous from the aspect of treatability (with the Combination, mobility, ductility etc. of other composition) when forming film, thus number-average molecular weight is preferably less than 1,000,000, is more preferably less than 500,000, more preferably less than 200,000.Said number-average molecular weight is the value calculated as follows herein: use that to possess at least 1 exclusion limit molecular weight be that the gel permeation chromatography of the post of more than 1,000 ten thousand measures, utilize the reference materials such as polystyrene, hold-time will be converted into molecular weight, calculate thus.Those skilled in the art easily can obtain number-average molecular weight.Calculate after except the peak from solvent.
The content contributing to the key of thermotolerance performance is also relevant with above-mentioned number-average molecular weight Mn.By the quantity of the number-average molecular weight of resin divided by the sulphur atom of the formation nitrogen-carbon-sulfide linkage comprised in every 1 molecule and the quantity n of the Sauerstoffatom of formation nitrogen-carbon-oxygen bond 1and the value (Mn/n obtained 1) be preferably less than 300, be more preferably less than 200, more preferably less than 150.As mentioned above, the resin combination of present embodiment with the adaptation of metal in also can have effect, from the viewpoint of showing this effect, also preferably there is more above-mentioned key in every 1 molecule resin.On the other hand, when resin has too much above-mentioned key, particularly resin have above-mentioned formula (6) ~ (8), (11) ~ (14), (41), (42), (45), (46) or the structural unit represented by (47) time, the flexibility as one of film performance sometimes also can be impaired.From the viewpoint of this, Mn/n 1be preferably more than 50, be more preferably more than 70.N 1such as can calculate as follows: such as by infrared absorption spectrum or 1h-NMR etc. obtain the quantity X of this key of per unit weight (1g) resin 1(unit mol/g), according to formula: n 1=MnX 1calculated by above-mentioned number-average molecular weight (Mn).When resin comprises nitrogen-carbon-sulfide linkage and nitrogen-carbon-oxygen bond, n 1form the sulphur atom of each key and the sum of Sauerstoffatom.When resin has the structural unit of formula (6) ~ (8), the quantity sum of the structural unit represented by formula (6) ~ (8) comprised in every this resin of 1 molecule is n 2time, Mn/n 2be less than more than 50 300.N 2through type: n 2=X 2mn calculates.X 2the quantity sum of the structural unit represented by formula (6) ~ (8) comprised in this resin of every 1g, can by with X 1same method is obtained.
The structure arranged between said structure unit is not particularly limited, preferred carbonatoms be 1 ~ 25 aliphatic group, carbonatoms be the aromatic group of 6 ~ 25.Specifically, the residue for obtaining from middle removing 2 hydrogen atoms such as methane, ethane, propane, butane, pentane, hexane, octane, decane, dodecane, octadecane, hexanaphthene, cyclooctane, dimethyl cyclohexane, diethyl cyclohexane, trimethyl-cyclohexane, trimethylethyl hexanaphthene, dicyclohexyl methyl hydride, tetramethyl-dicyclohexyl methyl hydride, benzene,toluene,xylene, ethylbenzene, diethylbenzene, ditan, tetramethyl-ditan.It should be noted that, when there is isomer, also comprising this isomer.
Among these, preferably there is the resin of the structure represented by following formula (301) ~ (306).
(in formula, i represents the integer of 1 ~ 12, can be 1 ~ 10.)
The preferred manufacture method > of <
The resin that preferred 1st resin of present embodiment obtains preferably through following method, the method comprises the following steps: the compound making to have at least one functional group be selected from group that 1 valency group represented by following formula (1) ~ (5) forms reacts with at least one compound be selected from monoisocyanates, polyisocyanates, monoisothiocyanates and polyisothiocyanates.
-OH(1)-NH 2(2)
In this specification sheets, sometimes the group represented by above-mentioned formula (1) is called hydroxyl, group represented by above-mentioned formula (2) is called amino, group represented by above-mentioned formula (3) is called hydrazide group, group represented by above-mentioned formula (4) is called amino urea groups, the group represented by above-mentioned formula (5) is called sulfo-amino urea groups.The group of formula (2) defines as from the group that formula (3) ~ group of (5) is different.
Below, the example of the manufacture method of preferred 1st resin of present embodiment is described.
[compound preferably used]
The compound of at least one group had in more than 2 groups selecting free hydroxyl, amino, hydrazide group, amino urea groups and sulfo-amino urea groups to form is not particularly limited, as long as comprise more than 2 to select free hydroxyl (-OH), amino (-NH 2), hydrazide group (-C (=O)-NH-NH 2), amino urea groups (-NH-C (=O)-NH-NH 2), sulfo-amino urea groups (-NH-C (=S)-NH-NH 2) at least one group in the group that forms.Such as, following formula (70) or the compound represented by formula (71) can be used.
(in formula, R 12, R 13and R 14represent organic group independently of one another, R 15represent organic group or singly-bound, A 1and E 1represent the group in the group selecting free hydroxyl, amino, hydrazide group, amino urea groups, sulfo-amino urea groups composition independently of one another, B 1and D 1represent group, organic group or the hydrogen atom in the group selecting free hydroxyl, amino, hydrazide group, amino urea groups, sulfo-amino urea groups composition independently of one another, F 1represent hydrogen atom or organic group, d represents the integer of 2 ~ 1000, and e represents the integer of 1 ~ 3, and x represents the integer of more than 1, and y represents the integer of more than 0 or 1.With R more than 2 in a part 12, R 13, R 14, A 1, E 1, B 1, D 1, F 1and e can be the same or different respectively.
In above-mentioned formula, R 12preferably carbonatoms be the aliphatic group of 1 ~ 25, the carbonatoms that replaces with aromatic group (aromatics) be 7 ~ 25 aliphatic group or carbonatoms be the aromatic group of 6 ~ 25.R 12concrete example be remove the residue after 1 hydrogen atom from methane, ethane, propane, butane, pentane, hexane, octane, decane, dodecane, octadecane, hexanaphthene, cyclooctane, dimethyl cyclohexane, diethyl cyclohexane, trimethyl-cyclohexane, trimethylethyl hexanaphthene, dicyclohexyl methyl hydride, tetramethyl-dicyclohexyl methyl hydride, benzene,toluene,xylene, ethylbenzene, diethylbenzene, ditan, tetramethyl-ditan etc.In this specification sheets, " carbonatoms replaced with aromatic group is the aliphatic group of 7 ~ 25 " is the group of the combination comprising aromatic group and aliphatic group, aromatic group and aliphatic group comprise the heteroatomss such as Sauerstoffatom, nitrogen-atoms, sulphur atom sometimes, the carbon atom comprised in this group add up to 7 ~ 25.Other same term defines similarly.
In above-mentioned formula, R 13and R 14preferably carbonatoms be the aliphatic group of 2 ~ 25, the carbonatoms that replaces with aromatic group be 7 ~ 25 aliphatic group or carbonatoms be the aromatic group of 8 ~ 25.R 13and R 14concrete example be remove the residue after 3 hydrogen atoms from ethane, propane, butane, pentane, hexane, octane, decane, dodecane, octadecane, hexanaphthene, cyclooctane, dimethyl cyclohexane, diethyl cyclohexane, trimethyl-cyclohexane, trimethylethyl hexanaphthene, dicyclohexyl ethane, ethylbenzene, diethylbenzene, diphenylethane, tetramethyl-diphenylethane etc.
In above-mentioned formula, R 15represent organic group or singly-bound, when for organic group, the aromatic hydrocarbyl that the alkylidene group be carbonatoms being 1 ~ 25, carbonatoms are 6 ~ 25 or following formula (72) or the group represented by formula (73).
(in formula, R 16, R 17and R 18represent independently of one another carbonatoms be 1 ~ 10 alkylidene group, carbonatoms be 6 ~ 10 aromatic hydrocarbyl or singly-bound, z represents the integer of 1 ~ 10.)
R 15to be carbonatoms be 1 ~ 25 alkylidene group or carbonatoms when being the aromatic hydrocarbyl of 6 ~ 25, R 15be specially the residue after removing 2 hydrogen atoms from methane, ethane, propane, butane, propane, hexane, octane, decane, dodecane, octadecane, hexanaphthene, cyclooctane, dimethyl cyclohexane, diethyl cyclohexane, trimethyl-cyclohexane, trimethylethyl hexanaphthene, dicyclohexyl methyl hydride, tetramethyl-dicyclohexyl methyl hydride, benzene,toluene,xylene, ethylbenzene, diethylbenzene, ditan, tetramethyl-ditan etc.
R 15for singly-bound represents, R 15do not exist as group, but R 13with E 1there is bonding.Below, for said in this specification sheets " singly-bound ", define equally and use.
In above-mentioned formula (72) and formula (73), R 16, R 17and R 18from methane, ethane, propane, butane, pentane, hexane, octane, decane, dodecane, octadecane, hexanaphthene, cyclooctane, dimethyl cyclohexane, diethyl cyclohexane, trimethyl-cyclohexane, trimethylethyl hexanaphthene, dicyclohexyl methyl hydride, tetramethyl-dicyclohexyl methyl hydride, benzene,toluene,xylene, ethylbenzene, diethylbenzene, ditan, tetramethyl-ditan etc., preferably remove the residue after 2 hydrogen atoms.When there is isomer, also comprise this isomer.
In above-mentioned formula (71), B 1, D 1and F 1when for organic group, this organic group is preferably alkyl that carbonatoms is 1 ~ 25, aromatic hydrocarbyl that carbonatoms is 6 ~ 25 or the group represented by following formula (74) ~ (76).
(in formula, R 19, R 20, R 21independently of one another represent carbonatoms be 1 ~ 10 alkylidene group or carbonatoms be the aromatic group of 6 ~ 10, z represents the integer of 1 ~ 10.)
In above-mentioned formula (74) ~ (76), R 19, R 20and R 21preferably carbonatoms be 1 ~ 25 alkylidene group or carbonatoms be the aromatic hydrocarbyl of 6 ~ 25.R 19, R 20and R 21be specially the residue after removing 2 hydrogen atoms from methane, ethane, propane, butane, pentane, hexane, octane, decane, dodecane, octadecane, hexanaphthene, cyclooctane, dimethyl cyclohexane, diethyl cyclohexane, trimethyl-cyclohexane, trimethylethyl hexanaphthene, dicyclohexyl methyl hydride, tetramethyl-dicyclohexyl methyl hydride, benzene,toluene,xylene, ethylbenzene, diethylbenzene, ditan, tetramethyl-ditan etc.When there is isomer, also comprise this isomer.
The concrete example of the compound of at least 1 functional group in the group comprising and select free hydroxyl, amino, hydrazide group, amino urea groups and sulfo-amino urea groups to form is shown below.
There is as (a) compound of hydroxyl, the polyvalent alcohols such as ethylene glycol, propylene glycol, tetramethylolmethane can be exemplified and there is the polyvalent alcohol of repeating unit.
As the example of polyvalent alcohol, acrylic polyol, polyolefin polyhydric alcohol, polyvinyl alcohol etc. can be enumerated.Acrylic polyol by make to have the one matter of the monomer containing ethylenic unsaturated link(age) of hydroxyl or mixture and can with other one matter containing the monomer of ethylenic unsaturated link(age) of its copolymerization or mixture copolymerization and obtain.
As the monomer containing ethylenic unsaturated link(age) with hydroxyl, such as, can enumerate Hydroxyethyl acrylate, Propylene glycol monoacrylate, hy-droxybutyl, hydroxyethyl methylacrylate, Rocryl 410, methacrylate etc.Be preferably Hydroxyethyl acrylate, hydroxyethyl methylacrylate.
As with other of above-mentioned monomer copolymerization containing the monomer of ethylenic unsaturated link(age), can enumerating the acrylate such as the just own ester of methyl acrylate, ethyl propenoate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, vinylformic acid, cyclohexyl acrylate, ethyl acrylate, lauryl acrylate, benzyl acrylate, phenyl acrylate; The methacrylic esters such as the just own ester of methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate, isopropyl methacrylate, methacrylic acid normal-butyl, Propenoic acid, 2-methyl, isobutyl ester, methacrylic acid, cyclohexyl methacrylate, methacrylic acid-2-ethylhexyl, lauryl methacrylate(LMA), benzyl methacrylate, phenyl methacrylate; The unsaturated carboxylic acids such as vinylformic acid, methacrylic acid, toxilic acid, methylene-succinic acid; The unsaturated amides such as acrylamide, Methacrylamide, N,N methylene bis acrylamide, diacetone acrylamides, methyl ethyl diketone Methacrylamide, maleinamide, maleimide; And the ethene base system monomer such as methacrylic acid acid glycidyl ester, vinylbenzene, Vinyl toluene, vinyl-acetic ester, vinyl cyanide, dibutyl fumarate; Vinyltrimethoxy silane, vinyl methyl dimethoxysilane, γ-(methyl) acryloxypropyl Trimethoxy silane etc. has the ethene base system monomer etc. of hydrolyzable silyl group.
As polyolefin polyhydric alcohol, such as, can enumerate the polyhutadiene, hydrogenated butadiene polymer, polyisoprene, hydrogenated polyisoprene etc. with more than 2 hydroxyls.The hydroxyl value (being hereinafter average number of hydroxyl) that statistics 1 molecule of polyvalent alcohol has is preferably more than 2.By making the average number of hydroxyl of polyvalent alcohol be more than 2, the reduction of the cross-linking density of obtained film can be suppressed.
As polyvinyl alcohol, can enumerate: the polyvinyl alcohol that the polyvinylesters obtained being polymerized by vinyl ester carries out saponification and obtains; At the main chain graft copolymerization comonomer of polyvinyl alcohol and the modified polyvinyl alcohol obtained; Modified polyvinyl alcohol manufactured by saponification is carried out to the modified polyvinyl ester making vinyl ester and comonomer carry out copolymerization and obtain; The aldehydes such as part formaldehyde, butyraldehyde, phenyl aldehyde of the hydroxyl of unmodified polyethylene alcohol or modified polyvinyl alcohol is carried out the so-called polyvinyl acetal resin etc. be cross-linked.
As the above-mentioned vinyl ester used in the manufacture of polyvinyl alcohol, such as, can enumerate vinyl-acetic ester, vinyl formate, propionate, vinyl butyrate, new vinyl acetate acid, tertiary ethylene carbonate, vinyl laurate, stearic acid vinyl ester, vinyl benzoate etc.Wherein, from the viewpoint of the ease of manufacturing of polyvinyl alcohol, obtain easiness, cost etc., preferred vinyl-acetic ester.In addition, the above-mentioned comonomer that uses in the manufacture of modified polyvinyl alcohol mainly carries out copolymerization with the object that is modified as of polyvinyl alcohol, uses in the scope not damaging purport of the present invention.As such comonomer, such as, can enumerate the olefines such as ethene, propylene, 1-butylene, iso-butylene; Vinylformic acid or its salt; The esters of acrylic acids such as methyl acrylate, ethyl propenoate, propyl acrylate (comprising isomer), butyl acrylate (comprising isomer), Octyl acrylate (comprising isomer), dodecylacrylate (comprising isomer); Methacrylic acid or its salt; The methyl acrylic esters such as methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate (comprising isomer), butyl methacrylate (comprising isomer), Octyl methacrylate (comprising isomer), lauryl methacrylate (comprising isomer), octadecyl methacrylate (comprising isomer); Acrylamide, N methacrylamide, N-ethyl acrylamide, N,N-DMAA, diacetone-acryloamide(DAA), acrylamide propane sulfonic acid or its salt, acrylamide propyl dimethylamine or the acrylamide derivative such as its salt, N hydroxymethyl acrylamide or derivatives thereof; Methacrylamide, N-methyl methacrylamide, N-ethyl methacrylamide, Methacrylamide propanesulfonic acid or its salt, Methacrylamide diemethylamine or the methacrylamide derivatives such as its salt, N-methylol methacrylamide or derivatives thereof; The N-vinylamide classes such as N-vinyl formamide, N-vinyl acetamide, NVP; The vinyl ethers such as methylvinylether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl-ethylene base ether, n-butyl vinyl ether, IVE, tert-Butyl vinyl ether, dodecyl vinyl, stearyl vinyl ether; The nitrile such as vinyl cyanide, methacrylonitrile; The ethylene halide classes such as vinylchlorid, vinylidene chloride, vinyl fluoride, vinylidene fluoride; The allylic cpd such as allyl acetate, chlorallylene; Toxilic acid or its salt or ester; Methylene-succinic acid or its salt or ester; The vinyl silyl groups compounds such as vinyltrimethoxy silane; Isopropyl acetate alkenyl esters etc.Wherein, preferred alpha-olefin (such as, carbonatoms is the alpha-olefin etc. of 2 ~ 30), unsaturated carboxylic acid or derivatives thereof, unsaturated sulfonic acid or derivatives thereof, more preferably alpha-olefin, particularly preferably ethene.Based on the mole number of the entire infrastructure unit of formation modified polyvinyl alcohol, the modification amount based on comonomer in modified polyvinyl alcohol is preferably less than 15 % by mole, is more preferably less than 5 % by mole.
In above cited polyvalent alcohol, preferred acrylic polyol, polyester polyol.
There is as (b) concrete example of amino compound, quadrol can be enumerated, propylene diamine, butanediamine, triethylenediamine, 1, 6-hexanediamine, 4, 4 '-diamino-dicyclohexyl methane, piperazine, 2-methylpiperazine, isophorone diamine, norcamphane diamines, phenylenediamine, 4, 4 '-benzidine, 1, two (3-amino-benzene oxygen) benzene of 3-, 3, 3 '-diaminodiphenylsulfone(DDS), diethyl toluene diamine, the Diamines such as dianiline, bis hexamethylene triamine, diethylenetriamine, Triethylenetetramine (TETA), tetren, pentamethylene hexamine, 4 sub-propyl-5-amines etc. have more than 3 the amino polynary amines of chain, 1, 4, 7, 10, 13, 16-hexanitrogen heterocycle octadecane, 1, 4, 7, 10-tetraazacyclododecane decane, 1, 4, 8, 12-tetraazacyclododecane pentadecane, 1, 4, 8, the cyclic polyol amines such as 11-tetraazacyclododecane tetradecane, polyallylamine, polyvinylamine, the polymkeric substance shape polyamines such as the polyamine represented by following formula (77) ~ (80).Wherein, preferred polyallylamine, polyvinylamine.It should be noted that, polyallylamine, polyvinylamine can use by the arbitrary substance manufactured by existing known method, are not particularly limited the polymerization degree etc.In addition, also can be the multipolymer with other monomer.
(in formula, g ' represents the integer of 2 ~ 70.)
(in formula, h ' represents the integer of 2 ~ 40,
I ', j ' represent the integer of 1 ~ 6 separately, and i ' and j ' sum are the integer of 2 ~ 7.)
(in formula, R 35represent the group be selected from the group be made up of hydrogen atom, methyl and ethyl,
S represents the integer of 0 or 1,
R, t, u represent the integer of more than 0 or 1 separately,
R and t and u sum are 5 ~ 90.)
There is as (c) compound of hydrazide group, such as, can enumerate saturated dicarboxylic acid two hydrazides that careless acid dihydrazide, acid dihydrazide, glutaric, amber acid dihydrazide, adipic dihydrazide, sebacic dihydrazide etc. have 2 ~ 18 carbon atoms; Mono-olefinic unsaturated dicarboxylic acid two hydrazides such as Malaysia acid dihydrazide, fumaric acid two hydrazides, methylene-succinic acid two hydrazides; Make to have the polyhydrazide etc. that the oligopolymer of carboxylic acid low alkyl group ester group and hydrazine or hydrazine hydrate react and obtain.In addition, also can for making the monomer containing ethylenic unsaturated link(age) with hydroxyl, such as Hydroxyethyl acrylate, Propylene glycol monoacrylate, hy-droxybutyl, hydroxyethyl methylacrylate, Rocryl 410, the polymkeric substance (also can be multipolymer) of methacrylate etc. and hydrazine reaction and the polymkeric substance that obtains, can also for making vinyl ester (such as, vinyl-acetic ester, vinyl formate, propionate, vinyl butyrate, new vinyl acetate acid, tertiary ethylene carbonate, vinyl laurate, stearic acid vinyl ester, vinyl benzoate etc.) polymkeric substance (also can be multipolymer) and hydrazine reaction and the polymkeric substance that obtains.
There is as (d) compound of amino urea groups, such as, can enumerate two Urea,amino-; Make the vulcabond such as hexamethylene diisocyanate or isophorone diisocyanate or multifunctional Urea,amino-of replacing hydrazine or above-mentioned illustrative hydrazine reaction by its derivative polyisocyanate compound and N, N-dimethylhydrazine etc. N, N-and obtaining etc.
There is as (e) compound of sulfo-amino urea groups, such as, can enumerate two thiosemicarbazide; The polyisothiocyanates compound making the diisothio-cyanate such as hexa-methylene diisothio-cyanate or isophorone diisothio-cyanate or derived by it and N, the multifunctional thiosemicarbazide etc. that N, the N-such as N-dimethylhydrazine replace hydrazine or above-mentioned illustrative hydrazine reaction and obtain.
As have hydroxyl compound example cited by polyvalent alcohol can for polyester polyol, polyether glycol, fluorine polyvalent alcohol, polycarbonate polyol, polyurethane polyol.
As polyester polyol, such as, can enumerate: make the one matter of the diprotic acid be selected from the group of the carboxylic acids such as succsinic acid, hexanodioic acid, sebacic acid, dimeracid, maleic anhydride, Tetra hydro Phthalic anhydride, m-phthalic acid, terephthalic acid or mixture and be selected from the one matter of the polyvalent alcohol in the group of ethylene glycol, propylene glycol, glycol ether, neopentyl glycol, TriMethylolPropane(TMP), glycerine etc. or the condensation reaction of mixture and the polyester polyol obtained; And such as by employing the ring-opening polymerization of the 6-caprolactone of polyvalent alcohol and the polycaprolactone class etc. obtained.
As polyether polyols alcohols, comprise: use the strong alkali catalysts such as the oxyhydroxide of such as lithium, sodium, potassium etc., alcoholate, alkylamine, to the one matter of the epoxy alkane such as one matter or mixture addition of ethylene oxide, propylene oxide, butylene oxide ring, epoxy cyclohexane, Styrene oxide 98min. of multi-hydroxy compound or mixture and the polyether polyols alcohols obtained; Make the polyether polyols alcohols that the polyfunctional compounds such as ethylenediamines and epoxy alkane react and obtain; And so-called polymer polyol alcohols acrylamide etc. being polymerized as medium by these polyethers and obtaining; Etc..
As multi-hydroxy compound, can enumerate
(1) Glycerol dimer, ditrimethylolpropane, tetramethylolmethane, Dipentaerythritol etc.,
(2) the sugar alcohol based compound such as tetrahydroxybutane, D-threitol, L-arabinose alcohol, ribitol, Xylitol, Sorbitol Powder, N.F,USP MANNITOL, melampyrum, rhamnitol,
(3) monose such as pectinose, ribose, wood sugar, glucose, seminose, semi-lactosi, fructose, sorbose, rhamnosyl, Fucose, ribodesose,
(4) disaccharides such as trehalose, sucrose, maltose, cellobiose, gentiobiose, lactose, melibiose,
(5) three carbohydrates such as raffinose, gentianose, melizitose,
(6) stachyose etc. four carbohydrate, etc.
Fluorine-containing polyvalent alcohol is the polyvalent alcohol containing fluorine in molecule, comprises the multipolymer of such as fluoroolefins, cyclic vinyl ether, hydroxyalkyl vinylether, monocarboxylic acid vinyl acetate etc. disclosed in Japanese Laid-Open Patent Publication 57-34107 publication, Japanese Laid-Open Patent Publication 61-275311 publication.
As polycarbonate polyol class, the material low molecular polylol polycondensation used in the low molecule carbonate products of the diaryl carbonates such as the alkylene carbonate such as dialkyl carbonate, ethylene carbonate, diphenyl carbonate such as methylcarbonate and so on and above-mentioned polyester polyol obtained can be enumerated.
Polyurethane polyol can by ordinary method, such as make polyvalent alcohol and polyisocyanates react and obtain.As the polyvalent alcohol without carboxyl, low-molecular-weight material can arrange and ethylene glycol, propylene glycol etc. are shown, the material of high molecular can exemplify acrylic polyol, polyester polyol, polyether glycol etc.
Can have and comprise one and select the compound of repeating unit of 1 group in the group of free hydroxyl, amino, hydrazide group, amino urea groups and sulfo-amino urea groups composition to be compound represented by following formula (81).
R 22——A 1(81)
(in formula, R 22represent organic group,
A 1represent the group that above-mentioned formula (70) defines.)
In above-mentioned formula, R 22preferably carbonatoms to be aliphatic group, the carbonatoms of 1 ~ 25 be 7 ~ 25 the aliphatic group replaced with aromatic group, carbonatoms be the aromatic group of 6 ~ 25.Specifically, R 22it is the residue remove 1 hydrogen atom from methane, ethane, propane, butane, pentane, hexane, octane, decane, dodecane, octadecane, hexanaphthene, cyclooctane, dimethyl cyclohexane, diethyl cyclohexane, trimethyl-cyclohexane, trimethylethyl hexanaphthene, dicyclohexyl methyl hydride, tetramethyl-dicyclohexyl methyl hydride, benzene,toluene,xylene, ethylbenzene, diethylbenzene, ditan, tetramethyl-ditan etc. after.When there is isomer, also comprise this isomer.
As the compound represented by above-mentioned formula (81), specifically, the oxy-compound such as methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, hexanol, octanol, decyl alcohol, dodecanol, Stearyl alcohol, hexalin, Lotka-Volterra circle system, dimethyl cyclohexanol, diethyl hexalin, cyclonol, trimethylethyl hexalin, dicyclohexyl methyl alcohol, tetramethyl-dicyclohexyl methyl alcohol, phenol, methylphenol, xylenol, ethylphenol, diethyl phenol can be enumerated, the amine such as ethamine, propylamine, butylamine, amylamine, hexylamine, octylame, decyl amine, n-Laurylamine, hexahydroaniline, cyclooctylamine, dimethylcyclohexylamine, phenyl amine, aminomethyl phenyl amine, 3,5-dimethylphenyl amine, ethylphenyl amine, diethyl phenyl amine, the hydrazides such as ethyl hydrazides, propyl group hydrazides, butyl hydrazides, amyl group hydrazides, hexyl hydrazides, octyl group hydrazides, decyl hydrazides, dodecyl hydrazides, cyclohexyl hydrazides, ring octyl group hydrazides, Dimethylcyclohexyl hydrazides, phenyl hydrazide, aminomethyl phenyl hydrazides, 3,5-dimethylphenyl hydrazides, ethylphenyl hydrazides, diethyl phenyl hydrazide, ethylamino urea, propylcarbamic urea, butyl Urea,amino-, pentyl amino urea, hexylamino urea, octyl amino urea, Decylamino urea, dodecylamino urea, Cyclohexylamino urea, ring octyl amino urea, Dimethylcyclohexyl Urea,amino-, Carbaphen, MethYlphenylamino urea, dimethylphenylamino urea, ethylphenyl Urea,amino-, the Urea,amino-such as diethyl Carbaphen, ethylenebis dithiocarbamate Urea,amino-, propyl dithiocarbamate Urea,amino-, butyl thiosemicarbazide, pentylthio Urea,amino-, hexyl thiosemicarbazide, octylsulfo Urea,amino-, decyl thiosemicarbazide, dodecyl thiosemicarbazide, cyclohexyl thio Urea,amino-, ring octylsulfo Urea,amino-, Dimethylcyclohexyl thiosemicarbazide, phenyl Urea,amino-, aminomethyl phenyl thiosemicarbazide, 3,5-dimethylphenyl thiosemicarbazide, ethylphenyl thiosemicarbazide, the thiosemicarbazides such as diethyl phenyl thiosemicarbazide.
Compound represented by above-mentioned formula (81) can compound represented by following formula (82).
R 23——R 15——E 1(82)
(in formula,
R 23represent that carbonatoms is the unsaturated fatty hydrocarbons base of 1 ~ 25,
R 15, E 1represent the group that above-mentioned formula (71) defines.)
Compound represented by above-mentioned formula (82) is more preferably the compound represented by following formula (83) ~ (85).
(in formula,
R 24, R 25and R 26represent that hydrogen atom or carbonatoms are the saturated hydrocarbyl of 1 ~ 6 independently of one another,
R 27, R 28, R 29and R 30represent that hydrogen atom, carbonatoms are the saturated hydrocarbyl of 1 ~ 6 independently of one another,
R 31represent that carbonatoms is saturated hydrocarbyl or the singly-bound of 1 ~ 6, E 1represent the group that above-mentioned formula (71) defines,
W represents the integer of 1 ~ 3.)
< isothiocyanate compound >
Isothiocyanate compound is the compound in 1 molecule with more than 1 isothiocyanate group, is classified as monoisothiocyanates and polyisothiocyanates.
In the resin combination of present embodiment, monoisothiocyanates is the compound in 1 molecule with 1 isothiocyanate group, is preferably the compound represented by following formula (30).
R 5——NCS(30)
(in formula, R 5represent organic group.)
In above-mentioned formula (30), R 5preferably carbonatoms be 1 ~ 25 aliphatic group or carbonatoms be the aromatic group of 6 ~ 25.R 5can be with aromatic group replace carbonatoms be the aliphatic group of 7 ~ 25.Specifically, R 5it is the residue remove 1 hydrogen atom from methane, ethane, propane, butane, pentane, hexane, octane, decane, dodecane, octadecane, hexanaphthene, cyclooctane, dimethyl cyclohexane, diethyl cyclohexane, trimethyl-cyclohexane, trimethylethyl hexanaphthene, dicyclohexyl methyl hydride, tetramethyl-dicyclohexyl methyl hydride, benzene,toluene,xylene, ethylbenzene, diethylbenzene, ditan, tetramethyl-ditan etc. after.When there is isomer, also comprise this isomer.
Specifically, compound represented by above-mentioned formula (1) can enumerate methane lsothiocyanates, ethane lsothiocyanates, propane lsothiocyanates, butane lsothiocyanates, pentane lsothiocyanates, hexane lsothiocyanates, octane lsothiocyanates, decane lsothiocyanates, dodecane lsothiocyanates, octadecane lsothiocyanates, hexanaphthene lsothiocyanates, cyclooctane lsothiocyanates, dimethyl cyclohexane lsothiocyanates, diethyl cyclohexane lsothiocyanates, trimethyl-cyclohexane lsothiocyanates, trimethylethyl hexanaphthene lsothiocyanates, dicyclohexyl methyl hydride lsothiocyanates, tetramethyl-dicyclohexyl methyl hydride lsothiocyanates, PITC, Tolueneisothiocyanate, dimethylbenzene lsothiocyanates, ethylbenzene lsothiocyanates, diethylbenzene lsothiocyanates, ditan lsothiocyanates, tetramethyl-ditan lsothiocyanates etc.
Compound represented by above-mentioned formula (30) can compound represented by following formula (86).
R 23——R 15——NCS(86)
(in formula, R 15, R 23represent the group that above-mentioned formula (82) defines.)
Compound represented by above-mentioned formula (30) is more preferably the compound represented by following formula (87) ~ (89).
(in formula,
R 24, R 25and R 26represent that hydrogen atom, carbonatoms are the saturated hydrocarbyl of 1 ~ 6 independently of one another,
R 27, R 28, R 29and R 30represent that hydrogen atom or carbonatoms are the saturated hydrocarbyl of 1 ~ 6 independently of one another,
R 31represent that carbonatoms is saturated hydrocarbyl or the singly-bound of 1 ~ 6,
W represents the integer of 1 ~ 3.)
As the concrete example of the compound represented by formula (87) ~ (89), can enumerate vinylformic acid Trapex, methacrylic acid Trapex, vinylformic acid (2-isothiocyanic acid ethyl) ester, methacrylic acid (2-isothiocyanic acid ethyl) ester, vinylformic acid (3-isothiocyanic acid propyl group) ester, methacrylic acid (3-isothiocyanic acid propyl group) ester, 2-isothiocyanato ethyl vinyl ether, 4-isothiocyanato butyl vinyl ether, to (isocyanatomethyl) vinylbenzene, to (isocyanatoethyl vinylbenzene) etc.
In the resin combination of present embodiment, polyisothiocyanates is the compound in 1 molecule with more than 2 isothiocyanate groups, such as, compound represented by following formula (32).
(in formula, R 6represent organic group,
A represents the integer of 2 ~ 1000.)
Preferred 1st mode of such polyisothiocyanates is the polymkeric substance of the repeating unit comprised represented by least 2 following formula (33).
(in formula, R 7represent organic group,
R 7represent organic group or singly-bound,
B represents the integer of more than 1,
G represents 1 or 2.With R more than 2 in a part 7, R 8, b and g can be the same or different respectively.)
As beyond the repeating unit that the polymkeric substance of preferred 1st mode of the polyisothiocyanates recorded can have represented by above-mentioned formula (33), one kind or two or more repeating unit herein.The end of this polymkeric substance is from polymerization starter, polymerization terminator, the group of terminal-modified dose, different because of the difference of manufacture method, only otherwise the purport violating present embodiment is not particularly limited.That is, preferred 1st mode of polyisothiocyanates is more preferably the compound represented by following formula (90).
(in formula, R 32represent organic group,
R 33represent organic group or singly-bound,
B 2and D 2represent at least a kind of group in the group that the organic group be selected from beyond by isothiocyanate group, isothiocyanate group and hydrogen atom form independently of one another,
G 1~ G xexpression can comprise or not comprise the organic group of isothiocyanate group, and x is the integer of more than 1, n xrepresent the integer of more than 1,
G represents 1 or 2,
F represents the integer of more than 1,
M represents the integer of more than 2.With R more than 2 in a part 32, R 33, f and g can be the same or different respectively.)
In above-mentioned formula (90), G 1~ G xrepresent the repeating unit beyond the repeating unit represented by above-mentioned formula (33).In addition, n xrepresent G xthe quantity of repeating unit.Such as, except the repeating unit represented by above-mentioned formula (43), G 1, G 2, G 3there is n respectively in these 3 kinds of repeating units 1, n 2, n 3time, be G 1n 1g 2n 2g 3n 3.
In above-mentioned formula (90), R 32preferably carbonatoms to be aliphatic group, the carbonatoms of 2 ~ 25 be 7 ~ 25 the aliphatic group replaced with aromatics or carbonatoms be the aromatic group of 8 ~ 25.R 32concrete example be from ethane, propane, butane, pentane, hexane, octane, decane, dodecane, octadecane, hexanaphthene, cyclooctane, dimethyl cyclohexane, diethyl cyclohexane, trimethyl-cyclohexane, trimethylethyl hexanaphthene, dicyclohexyl ethane, ethylbenzene, diethylbenzene, diphenylethane, tetramethyl-diphenylethane, ethanol, propyl alcohol, butanols, amylalcohol, hexanol, octanol, decyl alcohol, dodecanol, Stearyl alcohol, hexalin, Lotka-Volterra circle system, dimethyl cyclohexanol, diethyl hexalin, cyclonol, trimethylethyl hexalin, residue in dicyclohexyl ethanol etc. after removing 3 hydrogen atoms.
In above-mentioned formula (90), R 33represent organic group or singly-bound, when for organic group, the aromatic hydrocarbyl that the alkylidene group be carbonatoms being 1 ~ 25, carbonatoms are 6 ~ 25 or following formula (91) or the group represented by formula (92).
(in formula, R 34, R 36and R 37represent independently of one another carbonatoms be 1 ~ 10 alkylidene group, carbonatoms be 6 ~ 10 aromatic hydrocarbyl or singly-bound,
L represents the integer of 1 ~ 10.)
R 34to be carbonatoms be 1 ~ 25 alkylidene group, carbonatoms when being the aromatic hydrocarbyl of 6 ~ 25, specifically, be the residue after removing 2 hydrogen atoms from methane, ethane, propane, butane, pentane, hexane, octane, decane, dodecane, octadecane, hexanaphthene, cyclooctane, dimethyl cyclohexane, diethyl cyclohexane, trimethyl-cyclohexane, trimethylethyl hexanaphthene, dicyclohexyl methyl hydride, tetramethyl-dicyclohexyl methyl hydride, benzene,toluene,xylene, ethylbenzene, diethylbenzene, ditan, tetramethyl-ditan etc.
In above-mentioned formula (91), (92), R 34, R 36and R 37from methane, ethane, propane, butane, pentane, hexane, octane, decane, dodecane, octadecane, hexanaphthene, cyclooctane, dimethyl cyclohexane, diethyl cyclohexane, trimethyl-cyclohexane, trimethylethyl hexanaphthene, dicyclohexyl methyl hydride, tetramethyl-dicyclohexyl methyl hydride, benzene,toluene,xylene, ethylbenzene, diethylbenzene, ditan, tetramethyl-ditan etc., preferably remove the residue after 2 hydrogen atoms.It should be noted that, when there is isomer, also comprise this isomer.
In above-mentioned formula (90), B 2and D 2when for organic group, this organic group is preferably alkyl that carbonatoms is 1 ~ 25, aromatic hydrocarbyl that carbonatoms is 6 ~ 25 or the group represented by following formula (93) ~ (95).
(in formula, R 38, R 39and R 40independently of one another represent carbonatoms be 1 ~ 25 alkylidene group or carbonatoms be the aromatic group of 6 ~ 25,
P represents the integer of 1 ~ 10.)
In above-mentioned formula (93) ~ (95), R 38, R 39and R 40preferably carbonatoms is alkylidene group, the carbonatoms of 1 ~ 25 is the aromatic hydrocarbyl of 6 ~ 25, specifically, be remove the residue after 2 hydrogen atoms from methane, ethane, propane, butane, pentane, hexane, octane, decane, dodecane, octadecane, hexanaphthene, cyclooctane, dimethyl cyclohexane, diethyl cyclohexane, trimethyl-cyclohexane, trimethylethyl hexanaphthene, dicyclohexyl methyl hydride, tetramethyl-dicyclohexyl methyl hydride, benzene,toluene,xylene, ethylbenzene, diethylbenzene, ditan, tetramethyl-ditan etc.It should be noted that, when there is isomer, also comprise this isomer.
1st mode of the polyisothiocyanates above can be the polymkeric substance of the monoisothiocyanates such as represented by above-mentioned formula (41), and this polymkeric substance also can be the multipolymer with other monomer.Specifically, can enumerate: the multipolymer etc. of the multipolymer of the multipolymer of the multipolymer of the multipolymer of the multipolymer of vinylformic acid Trapex and methyl acrylate, methacrylic acid Trapex and methyl methacrylate, vinylformic acid (2-isothiocyanic acid ethyl) ester and methyl acrylate, methacrylic acid (2-isothiocyanic acid ethyl) ester and methyl methacrylate, vinylformic acid (3-isothiocyanic acid propyl group) ester and methyl acrylate, methacrylic acid (3-isothiocyanic acid propyl group) ester and methyl methacrylate.These compounds can utilize known method to manufacture.
In the resin combination of present embodiment, 2nd mode of polyisothiocyanates is following polyisothiocyanates, its there is structural unit represented by following formula (40) and be selected from group that the unit represented by following formula (41) ~ (47) form at least one structural unit, the nitrogen-atoms of formation polyisothiocyanates and carbon atom bonding.
SCN——R 9——(40)
(in formula, R 3represent organic group independently of one another,
R 4represent aliphatic group or aromatic group or aliphatic alkyl or aromatic hydrocarbyl,
The R of more than 2 3and R 4can be the same or different,
X 3represent Sauerstoffatom or sulphur atom.)
In above-mentioned formula (40), formula (41) ~ (47), R 3preferably carbonatoms is aliphatic group, the carbonatoms of 1 ~ 25 is the aromatic group of 6 ~ 25.Specifically, R 3it is the residue remove 2 hydrogen atoms from methane, ethane, propane, butane, pentane, hexane, octane, decane, dodecane, octadecane, hexanaphthene, cyclooctane, dimethyl cyclohexane, diethyl cyclohexane, trimethyl-cyclohexane, trimethylethyl hexanaphthene, dicyclohexyl methyl hydride, tetramethyl-dicyclohexyl methyl hydride, benzene,toluene,xylene, ethylbenzene, diethylbenzene, ditan, tetramethyl-ditan etc. after.When there is isomer, also comprise this isomer.
To the group-X comprised in above-mentioned formula (43), formula (45) 3-R 4be described.
As described later, in the manufacture of polyisothiocyanates of the present invention, generate the N represented by above-mentioned formula (43), N '-two replaces dithio allophanic acid key or the N-represented by above-mentioned formula (45) replaces-O-replacement thiocarbamate base (X 3situation for Sauerstoffatom) or N-replacement-S-replacement dithiocarbamate groups (X 3situation for sulphur atom) time, use oxy-compound or thio-alcohol.Base-X 3-R 4the group from this oxy-compound or thio-alcohol, when using oxy-compound, X 3for Sauerstoffatom, when using thio-alcohol, X 3for sulphur atom.
R 4it can be alkyl.Above-mentioned alkyl has at least one in aliphatic group and aromatic group, except carbon atom, can also comprise Sauerstoffatom and nitrogen-atoms etc.R 4aliphatic group or aromatic group, preferably carbonatoms be 1 ~ 22 aliphatic group or carbonatoms be the aromatic group of 6 ~ 22, be more preferably carbonatoms be 1 ~ 22 aliphatic group, carbonatoms be 1 ~ 22 aromatic group or carbonatoms be 1 ~ 22 aliphatic group and carbonatoms be the carbonatoms of the aromatic group bonding of 6 ~ 22 be the group of 7 ~ 22.As R 4concrete example, methyl can be enumerated, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, dodecyl, octadecyl, cyclopentyl, cyclohexyl, suberyl, ring octyl group, methylcyclopentyl, ethylcyclopentyl, methylcyclohexyl, ethylcyclohexyl, propylcyclohexyl, butylcyclohexyl, pentylcyclohexyl, hexyl cyclohexyl, Dimethylcyclohexyl, diethyl cyclohexyl, dibutyl cyclohexyl, phenyl, aminomethyl phenyl, ethylphenyl, propyl group phenyl, butyl phenyl, amyl group phenyl, hexyl phenyl, octyl phenyl, nonyl phenyl, cumyl phenyl, 3,5-dimethylphenyl etc.
Polyisothiocyanates in present embodiment can be the polyisothiocyanates compound shown in following formula (33) of a kind of the polyisothiocyanates as present embodiment being polymerized further and obtaining.
SCN——R 3-NCS(33)
(in formula, R 3represent organic group.)
R in above-mentioned formula (33) 3preferably carbonatoms is aliphatic group, the carbonatoms of 1 ~ 25 is the aromatic group of 6 ~ 25.R 3concrete example be remove the residue after 2 hydrogen atoms from methane, ethane, propane, butane, pentane, hexane, octane, decane, dodecane, octadecane, hexanaphthene, cyclooctane, dimethyl cyclohexane, diethyl cyclohexane, trimethyl-cyclohexane, trimethylethyl hexanaphthene, dicyclohexyl methyl hydride, tetramethyl-dicyclohexyl methyl hydride, benzene,toluene,xylene, ethylbenzene, diethylbenzene, ditan, tetramethyl-ditan etc.When there is isomer, also comprise this isomer.R 3be more preferably the group represented by following formula (300) ~ (306).
(in formula, i represents the integer of 1 ~ 12, can be 1 ~ 10.)
As the compound represented by above-mentioned formula (33), preferably can enumerate hexa-methylene diisothio-cyanate, isophorone diisothio-cyanate, 4 further, 4 '-dicyclohexyl methyl hydride diisothio-cyanate, 4,4 '-ditan diisothio-cyanate, toluene diisothio-cyanate (Isomers), naphthalene diisothio-cyanate (Isomers) etc.
As the compound represented by above-mentioned formula (33), also phenylene diisothio-cyanate, 4 can be enumerated, 4 '-diisothiocyanic acid base diphenyl ether, 1, two (3-isothiocyanatophenoxy) benzene, 3 of 3-, 3 '-diisothiocyanic acid root closes sulfobenzide, diethyltoluene diisothio-cyanate etc.
Below, the resin (polyisothiocyanates) obtained the compound polymerization made represented by above-mentioned formula (33) is recorded.It should be noted that, in following record, sometimes the compound represented by above-mentioned formula (33) is designated as " monomer " with the implication of the compound before polymerization.
The polyisothiocyanates manufactured about the polymerization by " monomer " represented by above-mentioned formula (33), when it manufactures, uses oxy-compound and/or thio-alcohol as auxiliary material.
As oxy-compound, methyl alcohol can be enumerated, ethanol, propyl alcohol, butanols, amylalcohol, hexanol, enanthol, octanol, decyl alcohol, dodecanol, cyclopentanol, hexalin, suberyl alcohol, Lotka-Volterra circle system, methylcyclopentanol, ethyl cyclopentanol, methyl-cyclohexanol, ethyl cyclohexanol, cyclohexyl alcohol, butylcyclohexyl alcohol, amyl group hexalin, hexyl hexalin, dimethyl cyclohexanol, diethyl hexalin, dibutyl hexalin, phenol, methylphenol, ethylphenol, propylphenol, butylphenol, amyl phenol, hexylphenol, octyl phenol, nonylphenol, cumyl phenol, xylenol, methylethyl phenol, methyl-propyl phenol, methyl butyl phenol, methyl amyl phenol, diethyl phenol, ethyl propyl phenol, ethyl-butyl phenol, dipropyl phenol, dicumyl phenol, pseudocuminol, triethyl phenol, naphthols etc.
Also spent glycol, 1 can be made, 2-propylene glycol, 1, ammediol, 1,3 butylene glycol, BDO, 2,3-butyleneglycol, 1,6-hexylene glycol, neopentyl glycol, neopentyl glycol hydroxypivalic acid ester, 2-ethyl-1,3-hexylene glycol, TriMethylolPropane(TMP), glycerine, 1,2, the polyester polyol, polyether glycol etc. of the low-molecular weight compounds such as 6-hexanetriol and molecular weight about 200 ~ 10,000.
As thio-alcohol, thiomethyl alcohol can be enumerated, sulfur alcohol, propylmercaptan, butyl sulfhydryl, pentan-thiol, hexylmercaptan, heptanthiol, spicy thioalcohol, decyl mercaptan, Dodecyl Mercaptan, cyclopentyl mercaptan, cyclohexylmercaptan, ring heptanthiol, cyclooctasulfur alcohol, methyl cyclopentyl mercaptan, ethyl cyclopentyl mercaptan, methyl cyclohexane mercaptan, cyclohexyl mercaptan, cyclohexyl mercaptan, butylcyclohexyl mercaptan, amyl group cyclohexylmercaptan, hexyl cyclohexylmercaptan, dimethyleyelohexane mercaptan, diethyl cyclohexylmercaptan, dibutyl cyclohexylmercaptan, thiophenol, methylbenzene phenyl-sulfhydrate, ethyl thiophenol, propylbenzene thiophenol, butylbenzene thiophenol, amylbenzene thiophenol, hexyl benzene thiophenol, octyl group thiophenol, nonyl benzene thiophenol, cumyl thiophenol, thiophenol dimethyl benzene, methylethyl thiophenol, methyl-propyl thiophenol, methyl butyl thiophenol, methyl amyl thiophenol, diethylbenzene thiophenol, ethyl propyl thiophenol, ethyl-butyl thiophenol, dipropyl thiophenol, dicumyl thiophenol, trimethylbenzenethiol, triethylbenzene thiophenol, thionaphthol etc.
When using oxy-compound, the isothiocyanate group/hydroxyl equivalent of above-mentioned oxy-compound and " monomer " represented by above-mentioned formula (33) is than selecting from the value of about 10 ~ 100 according to object.During use thio-alcohol too, isothiocyanate group/thiol equivalence ratio can be selected from the value of about 10 ~ 100 according to object.
The polyreaction of the monomer of through type (33), can form the different trithiocyanuric acid ester group represented by formula (41).As the different trithiocyanuric acid esterifying catalyst for the formation of the different trithiocyanuric acid ester group represented by formula (41), be preferably quaternary ammonium salt, be more preferably quaternary ammonium hydroxide, quaternary ammonium carboxylic acid, more preferably quaternary ammonium carboxylic acid.As concrete example, the tetra-alkyl ammonium hydroxides such as Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TBAH can be enumerated; The organic monoacid salt etc. such as acetic acid tetramethyl ammonium, acetic acid tetraethyl-ammonium salt, tetrabutylphosphoniuacetate acetate ammonium salt.Also the metal-salt etc. of the alkyl carboxylic acid such as acetic acid, valeric acid, isovaleric acid, caproic acid, sad, TETRADECONIC ACID can be used, from the viewpoint of reducing consumption, preferred organic salt of weak acid etc.
As the oxy-compound of the above-mentioned different trithiocyanuric acid esterifying catalyst of dilution, such as methyl alcohol, ethanol, n-butyl alcohol, 2-butanols, 2-methyl isophthalic acid-propyl alcohol, 1 can be enumerated, 2-propylene glycol, 1, ammediol, 1,3-butyleneglycol, 1, the phenolic hydroxyl group compounds such as alcohol hydroxyl group compound, phenol, cresols, xylenol, pseudocuminol such as 4-butyleneglycol, 2,3-butanediol, glycerine, hexalin.From the crystalline aspect of the polyisocyanates obtained thus, preferred 2-butanols, 2-methyl isophthalic acid-propyl alcohol, 1,3 butylene glycol, 2,3-butanediol etc. have the alcohol of side chain.In addition, also can mix two or more.It should be noted that, thio-alcohol can be used to replace this oxy-compound.
When the monomer making the monomer represented by above-mentioned formula (33) or isothiocyanate group oxy-compound has been carried out urethane reacts under the existence of above-mentioned different trithiocyanuric acid esterifying catalyst, carry out according to the condition being 1 ~ 20 quality % by the concentration of the different trithiocyanuric acid esterifying catalyst after above-mentioned oxy-compound dilution.Concentration is preferably 1 ~ 10 quality %.If concentration is more than 1 quality %, the amount of the oxy-compound accompanied with different trithiocyanuric acid esterifying catalyst can not become too much, and the polyisothiocyanates obtained and the physical property of film formed thus are difficult to reduce.If concentration is below 20 quality %, the co catalysis effect of the oxy-compound accompanied can not reduce, its result, is difficult to the increase of consumption and the painted of polyisothiocyanates etc. that cause different trithiocyanuric acid esterifying catalyst.
Except different trithiocyanuric acid esterifying catalyst, because of the acidic component that contains of trace in the raw materials such as the monomer represented by above-mentioned formula (33), except the situation of inactivation, the consumption of different trithiocyanuric acid esterifying catalyst is 1ppm ~ 10% relative to the weight of monomer diisothio-cyanate, is preferably 10ppm ~ 5%.If this amount more than 1ppm, then can give full play to the function as different trithiocyanuric acid esterifying catalyst.If this amount less than 3%, then the addition for the acid phosphatase compound and acid phosphoesterase compound (aftermentioned) that make different trithiocyanuric acid esterifying catalyst inactivation reduces.
Can use during reaction or not use solvent, but by using the solvent with isothiocyanate group without reactive behavior, the control of reaction becomes and is more prone to.
As the example of solvent, the esters such as ethyl acetate, butylacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate or ethers, benzene,toluene,xylene, ethylbenzene, trimethylbenzene etc. can be used aromatic hydrocarbon based.Certainly, also two or more solvent can be used.
Different trithiocyanuric acid esterification 30 DEG C ~ 120 DEG C, preferably carry out at 50 DEG C ~ 100 DEG C.The carrying out of reaction can by reaction solution 1h-NMR analyzes and confirms.
When reaction reaches desired transformation efficiency, make catalyst deactivation by dropping into reaction terminating agent, thus stopped reaction.It is suitable that transformation efficiency is selected in the scope of 10 ~ 60%, is preferably 10 ~ 30%.During low conversion rate, the polyisothiocyanates that viscosity is lower can be obtained, but from the viewpoint of productivity, preferred transformation efficiency is more than 10%.On the other hand, if transformation efficiency is less than 60%, then the viscosity of polyisothiocyanates can not become too high, thus preferably.
Transformation efficiency can be obtained by following formula.
? 1in H-NMR spectrogram, the peak of the methyl of tetramethylsilane is set to 0ppm, calculates transformation efficiency according to following formula by the integrated value (B) at the integrated value (A) at the peak of 3.5ppm and the peak of 4.8ppm.
Transformation efficiency (%)=B/ (A+B) × 100
As the terminator of different trithiocyanuric acid esterification, use the compound of more than a kind in acid phosphatase compound and acid phosphoesterase compound.
Acid phosphatase compound is mineral acid, can enumerate such as phosphoric acid, phosphorous acid, ortho phosphorous acid, diphosphorous acid, Hypophosporous Acid, 50, tetra-sodium, peroxide phosphoric acid etc.Acid phosphatase compound is preferably phosphoric acid.
Acid phosphoesterase compound is the compound with acidic-group and ester group, can enumerate such as carbonatoms be 2 ~ 8 monoalkyl phosphoric acid esters, monoalkyl phosphorous acid ester or carbonatoms be 4 ~ 16 dialkyl phosphate, dialkyl phosphites or didodecyl phosphate, diphenyl phosphate, mono phosphoric acid ester lauryl, mono phosphoric acid ester phenyl ester, phosphorous acid two lauryl, diphenyl phosphite, phosphorous acid list lauryl, phosphorous acid monophenyl etc.Acid phosphoesterase compound be preferably carbonatoms be 3 ~ 8 monoalkyl phosphoric acid esters or carbonatoms be the dialkyl phosphate of 6 ~ 16, be more preferably dioctylphosphoric acid ester, mono-octyl phosphate.Among these, preferably use acid phosphatase compound.The addition of acid phosphatase compound is preferably 1 ~ 10 equivalent relative to the stoichiometry of different trithiocyanuric acid esterifying catalyst, is more preferably 1 ~ 6 equivalent.If more than addition 1 equivalent, the abundant inactivation of different trithiocyanuric acid esterifying catalyst can be made.If below addition 10 equivalent, the filtration of the insolubles produced also can not become difficulty, thus preferably.
The polyisothiocyanates of present embodiment can compound represented by following formula (96) ~ (99).
(in formula, h ' represents the integer of 2 ~ 40,
I ', j ' represent the integer of 1 ~ 6 separately, and i ' and j ' sum are the integer of 2 ~ 7.)
(in formula, k represents the integer of 1 ~ 4.)
(in formula, R 35represent the group be selected from the group be made up of hydrogen atom, methyl, ethyl,
S represents the integer of 0 or 1,
R, t, u represent the integer of more than 0 or 1 separately, and r and t and u sum are 5 ~ 90.)
(in formula, v represents the integer of 2 ~ 70.)
[reaction method]
The method that the compound making to have at least one group in the group selecting free hydroxyl, amino, hydrazide group, amino urea groups and sulfo-amino urea groups to form and the lsothiocyanates (can be monoisothiocyanates, also can be polyisothiocyanates) of present embodiment react is described.
The resin combination of present embodiment can contain all following resins.
1. make the resin that the compound of at least a kind of group had in more than 2 groups selecting free hydroxyl, amino, hydrazide group, amino urea groups and sulfo-amino urea groups to form and monoisothiocyanates react and obtain;
2. make the resin that the compound of the a kind of group had in 1 group selecting free hydroxyl, amino, hydrazide group, amino urea groups and sulfo-amino urea groups to form and polyisothiocyanates react and obtain;
3. make the resin that the compound of at least a kind of group had in more than 2 groups selecting free hydroxyl, amino, hydrazide group, amino urea groups and sulfo-amino urea groups to form and polyisothiocyanates react and obtain.
In all cases, the combination of the functional group of reacting is all identical, all can carry out according to method described herein.
In the following description, in order to make reaction easy to understand that reaction formula is shown, this reaction formula is recorded for monofunctional compound, but certainly also carries out same reaction when polyfunctional compound.
[with the reaction of compound with hydroxyl]
There is the compound of hydroxyl and the reaction of lsothiocyanates represented by following formula (100).
(in formula, R 41, R 42represent organic group independently of one another.)
Reaction can be implemented in the presence of solvent, also can solvent not in the presence of implement.About the solvent of use when carrying out in the presence of solvent, be preferably the solvent of inertia for hydroxyl and isothiocyanate group; Although or with lsothiocyanates radical reaction, the solvent that speed is extremely slow for goal response.As preferred solvent, the hydrocarbon compounds such as pentane, hexane, heptane, octane, nonane, decane, dodecane, the tetradecane, pentadecane, n-Hexadecane, octadecane, nonadecane can be enumerated; The hydrocarbon compounds such as ether, tetrahydrofuran (THF), Octyl Ether, nonyl ethers, decyl ethers, lauryl ether, myristyl ether, pentadecyl ether, cetyl ether, octadecyl ether, tetraethyleneglycol dimethyl ether are by the ethers of ehter bond bonding; The hydrocarbon compounds such as dimethyl sulphide, diethyl thioether, butyl sulfide, dihexyl thioether, octyl group thioether, nonyl thioether, decyl thioether, dodecyl thioether, tetradecyl thioether, pentadecyl thioether, hexadecyl thioether, octadecyl thioether, nonadecyl thioether are by the thioether class of thioether bond bonding; The aromatic hydrocarbon compound such as benzene, toluene, ethylbenzene, butylbenzene, amylbenzene, hexyl benzene, octyl group benzene, biphenyl, terphenyl, diphenylethane, (aminomethyl phenyl) diphenylphosphino ethane, dimethyl diphenyl, benzyl toluene; The aromatic hydrocarbon compound such as diphenyl ether, two (methyl-benzyl) ether, two (Ethylbenzyl) ether, two (butyl benzyl) ether, two (amyl group benzyl) ether, two (hexyl benzyl) ether, two (octyl group benzyl) ether, diphenyl ether, dibenzyl ether is by the aromatic series ethers of ehter bond bonding; Diphenyl sulfide, two (methyl-benzyl) thioether, two (Ethylbenzyl) thioether, two (butyl benzyl) thioether, two (amyl group benzyl) thioether, two (hexyl benzyl) thioether, two (octyl group benzyl) thioether, aromatic hydrocarbon compound such as two (aminomethyl phenyl) thioether, dibenzyl sulfide etc. are by the aromatic thioether class of thioether bond bonding; The hydrocarbon compounds such as anisole, phenetole, butyl phenyl ether, dimethoxy benzene, diethoxybenzene, Dibutoxy Benzene and aromatic hydrocarbon compound are by the compound of ehter bond bonding; The halogenide such as methyl chloride, monochloroethane, chloropentane, chloro-octane, monobromethane, monobromethane, bromo pentane silane, bromooctane, ethylene dichloride, dichloropentane, two chloro-octanes, ethylene dibromide, dibromo pentane, two bromooctanes, chlorobenzene, bromobenzene, dichlorobenzene, dibromobenzene; The ketones such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), diisobutyl ketone, pimelinketone; The amidess such as METHYLPYRROLIDONE, N,N-dimethylacetamide, DMF; The sulfoxide types such as dimethyl sulfoxide (DMSO); Water.
Temperature of reaction is not particularly limited, can carries out the scope of 0 DEG C ~ 300 DEG C.About the reaction times, the arbitrary reaction times can be set, such as, infrared spectrometer can be utilized to follow the trail of the remaining quantity of isothiocyanate group, stopped reaction after reaching desired remaining quantity.
In general, the reaction of hydroxyl and isothiocyanate group is slow, thus can use catalyzer.Catalyzer is Lewis acid and the compound generating lewis acidic transistion metal compound, organo-tin compound, copper race metal, zinc, iron family metal.As the concrete example of catalyzer, AlX can be enumerated 3, TiX 3, TiX 4, VOX 3, VX 5, ZnX 2, FeX 3, SnX 4lewis acid represented by (herein, X be halogen, acetoxyl group, alkoxyl group, aryloxy) and generate lewis acidic transistion metal compound; (CH 3) 3snOCOCH 3, (C 2h 5) SnOCOC 6h 5, Bu 3snOCOCH 3, Ph 3snOCOCH 3, Bu 2sn (OCOCH 3) 2, Bu 2sn (OCOC 11h 23) 2, Ph 3snOCH 3, (C 2h 5) 3snOPh, Bu 2sn (OCH 3) 2, Bu 2sn (OC 2h 5) 2, Bu 2sn (OPh) 2, Ph 2sn (CH 3) 2, (C 2h 5) 3snOH, PhSnOH, Bu 2snO, (C 8h 17) 2snO, Bu 2snCl 2, the represented organo-tin compound such as BuSnO (OH); CuCl, CuCl 2, CuBr, CuBr 2, CuI, CuI 2, Cu (OAc) 2, Cu (acac) 2, olefin acid copper, Bu 2cu, (CH 3o) 2cu, AgNO 3, AgBr, silver trinitrophenolate, AgC 6h 6clO 4the compound of Deng Tong race metal; Zn (acac) 2deng zn cpds; Fe (C 10h 8) (CO) 5, Fe (CO) 5, Fe (C 4h 6) (CO) 3, Co (trimethylbenzene) 2(PEt 2ph 2), CoC 5f 5(CO) 7, the iron family metal such as ferrocene compound etc. (Bu represents butyl, and Ph represents phenyl, and acac represents acetylacetone chelate part.)。
[with the reaction with amino compound]
There is the reaction of amino compound and lsothiocyanates represented by following formula (101).
(in formula, R 41, R 42for the group that above-mentioned formula (100) defines.)
Reaction can be implemented in the presence of solvent, also can solvent not in the presence of implement.About the solvent of use when carrying out in the presence of solvent, be preferably the solvent of inertia for amino and isothiocyanate group; Although or with lsothiocyanates radical reaction but the solvent that speed is extremely slow for goal response.As preferred solvent, the hydrocarbon compounds such as pentane, hexane, heptane, octane, nonane, decane, dodecane, the tetradecane, pentadecane, n-Hexadecane, octadecane, nonadecane can be enumerated; The hydrocarbon compounds such as ether, tetrahydrofuran (THF), Octyl Ether, nonyl ethers, decyl ethers, lauryl ether, myristyl ether, pentadecyl ether, cetyl ether, octadecyl ether, tetraethyleneglycol dimethyl ether are by the ethers of ehter bond bonding; The hydrocarbon compounds such as dimethyl sulphide, diethyl thioether, butyl sulfide, dihexyl thioether, octyl group thioether, nonyl thioether, decyl thioether, dodecyl thioether, tetradecyl thioether, pentadecyl thioether, hexadecyl thioether, octadecyl thioether, nonadecyl thioether are by the thioether class of thioether bond bonding; The aromatic hydrocarbon compound such as benzene, toluene, ethylbenzene, butylbenzene, amylbenzene, hexyl benzene, octyl group benzene, biphenyl, terphenyl, diphenylethane, (aminomethyl phenyl) diphenylphosphino ethane, dimethyl diphenyl, benzyl toluene; The aromatic hydrocarbon compound such as diphenyl ether, two (methyl-benzyl) ether, two (Ethylbenzyl) ether, two (butyl benzyl) ether, two (amyl group benzyl) ether, two (hexyl benzyl) ether, two (octyl group benzyl) ether, diphenyl ether, dibenzyl ether is by the aromatic series ethers of ehter bond bonding; Diphenyl sulfide, two (methyl-benzyl) thioether, two (Ethylbenzyl) thioether, two (butyl benzyl) thioether, two (amyl group benzyl) thioether, two (hexyl benzyl) thioether, two (octyl group benzyl) thioether, aromatic hydrocarbon compound such as two (aminomethyl phenyl) thioether, dibenzyl sulfide etc. are by the aromatic thioether class of thioether bond bonding; The hydrocarbon compounds such as anisole, phenetole, butyl phenyl ether, dimethoxy benzene, diethoxybenzene, Dibutoxy Benzene and aromatic hydrocarbon compound are by the compound of ehter bond bonding; The halogenide such as methyl chloride, monochloroethane, chloropentane, chloro-octane, monobromethane, monobromethane, bromo pentane silane, bromooctane, ethylene dichloride, dichloropentane, two chloro-octanes, ethylene dibromide, dibromo pentane, two bromooctanes, chlorobenzene, bromobenzene, dichlorobenzene, dibromobenzene; Water.
Temperature of reaction is not particularly limited, can carries out the scope of-50 DEG C ~ 250 DEG C.About the reaction times, the arbitrary reaction times can be set, such as, infrared spectrometer can be utilized to follow the trail of the remaining quantity of isothiocyanate group, stopped reaction after reaching desired remaining quantity.
In general, amino fast with the reaction of isothiocyanate group, thus do not need to use catalyzer, but do not negate use itself yet.As catalyzer, the catalyzer enumerated in above-mentioned [with the reaction of compound with hydroxyl] can be used in.
[with the reaction of compound with hydrazide group, amino urea groups or sulfo-amino urea groups]
There are different because of used compound of hydrazide group, amino urea groups or the compound of sulfo-amino urea groups and the reaction of lsothiocyanates, various reaction can occur, such as, can enumerate the reaction represented by following formula (102).
(in formula, R 41, R 42for the group that above-mentioned formula (100) defines,
Y represents-NH-base or CH 2-Ji,
Z represents Sauerstoffatom or sulphur atom.)
The reaction of the compound and lsothiocyanates with hydrazide group, amino urea groups or sulfo-amino urea groups can be implemented in the presence of solvent, also can solvent not in the presence of implement.About the solvent of use when carrying out in the presence of solvent, except the solvent enumerated in above-mentioned [with the reaction of compound with hydroxyl], the alcohols such as methyl alcohol, ethanol, propyl alcohol, butanols can also be used; The ester classes such as methyl acetate, ethyl acetate, propyl acetate, butylacetate, methoxy butyl acetate, cellosolve acetate, pentyl acetate, methyl lactate, ethyl lactate, n-Butyl lactate.
Temperature of reaction is not particularly limited, can carries out the scope of 0 DEG C ~ 300 DEG C.About the reaction times, the arbitrary reaction times can be set, such as, infrared spectrometer can be utilized to follow the trail of the remaining quantity of isothiocyanate group, stopped reaction after reaching desired remaining quantity.
Carry out under reaction in the presence of a catalyst, does not exist.When using catalyzer, the catalyzer enumerated in above-mentioned [with the reaction of compound with hydroxyl] can be used in.
There is the compound of hydrazide group or amino urea groups and lsothiocyanates when reacting, also preferably carry out heat treated further.By this heat treated, the effect of the mechanical characteristics such as rigidity, hardness, processibility, shock-resistance, flexural fatigue improving resin combination sometimes can be played.The principle playing this effect is still not clear, the present inventor infer may be due to: by heat treated, the reaction of bonding represented by following formula (103) or formula (104) on such as above-mentioned formula (102) the right and form ring structure in molecular chain.
(in formula, R 41, R 42, the group that defines for above-mentioned formula (102) of Y, Z.)
One of optimal way of the resin of present embodiment is for having the resin that more than 2 are selected from least a kind of structural unit in the group that the divalent group represented by following formula (6) ~ (8) forms.
(in formula, Y 1representing organic group, can be-NH-base.)
Y 1preferably carbonatoms be 1 ~ 12 aliphatic group or carbonatoms be the aromatic group of 6 ~ 12.Be the aliphatic group of 1 ~ 12 as carbonatoms, can enumerate by the derivative divalent group of the hydrocarbon compounds such as methane, ethane, propane, butane, pentane, hexane, octane, decane; Be there is by hexanaphthene, cyclooctane, cyclodecane, methylcyclohexane, ethylcyclohexane, butyl cyclohexane, dimethyl cyclohexane etc. the divalent group of the compound deriving of cyclic hydrocarbon group; And by the derivative divalent group of the aromatic hydrocarbon compounds such as benzene, toluene, ethylbenzene, butylbenzene, own benzene.
The resin of some modes has at least a kind of group be selected from group that the group represented by above-mentioned formula (6) ~ (8) forms in main chain backbone.Such as, resin has the structural unit represented by following formula (105) ~ (108).
(in formula, R 43represent organic group,
The R of more than 2 43can be the same or different,
J represents above-mentioned formula (6), (7) or the divalent group represented by (8), with R more than 2 in a part 43can be the same or different with J.)
Above-mentioned R 43preferably carbonatoms to be aliphatic group, the carbonatoms of 2 ~ 25 be 7 ~ 25 the aliphatic group replaced with aromatics or carbonatoms be the aromatic group of 8 ~ 25.As R 43concrete example, can enumerate from ethane, propane, butane, pentane, hexane, octane, decane, dodecane, octadecane, hexanaphthene, cyclooctane, dimethyl cyclohexane, diethyl cyclohexane, trimethyl-cyclohexane, trimethylethyl hexanaphthene, dicyclohexyl ethane, ethylbenzene, diethylbenzene, diphenylethane, tetramethyl-diphenylethane, ethanol, propyl alcohol, butanols, amylalcohol, hexanol, octanol, decyl alcohol, dodecanol, Stearyl alcohol, hexalin, Lotka-Volterra circle system, dimethyl cyclohexanol, diethyl hexalin, cyclonol, trimethylethyl hexalin, residue in dicyclohexyl ethanol etc. after removing 3 hydrogen atoms.
The resin combination of present embodiment is further preferably containing the resin represented by following formula (109).
(in formula, K 1~ K crepresent at least a kind of group be selected from the group be made up of above-mentioned formula (6) ~ (8) independently of one another,
L 1~ L crepresent the organic group that can contain or not containing the group in the group selecting free style (6) ~ (8) to form independently of one another, c represents the integer of more than 1,
M 1and M 2represent the organic group that can contain or not containing isothiocyanate group independently of one another,
W crepresent the integer of more than 1.)
In above-mentioned formula (109), w crepresent K c-L cthe quantity of repeating unit.Such as, by K 1-L 1and K 2-L 2when the resin that these 2 kinds of repeating units are formed, above-mentioned formula (109) is represented by following formula (110).
Be not particularly limited containing having more than 2 manufacture method being selected from the resin combination of the resin of at least one structural unit in the group that the group represented by above-mentioned formula (6) ~ (8) forms, such as, can by there is hydrazide group, amino urea groups or the compound of sulfo-amino urea groups and the reaction of lsothiocyanates and manufacturing.
The reaction of the compound and lsothiocyanates with hydrazide group, amino urea groups or sulfo-amino urea groups can be implemented in the presence of solvent, also can solvent not in the presence of implement.About the solvent of use when carrying out in the presence of solvent, except the solvent enumerated in above-mentioned [with the reaction of compound with hydroxyl], the alcohols such as methyl alcohol, ethanol, propyl alcohol, butanols can also be used; The ester classes such as methyl acetate, ethyl acetate, propyl acetate, butylacetate, methoxy butyl acetate, cellosolve acetate, pentyl acetate, methyl lactate, ethyl lactate, n-Butyl lactate.
Temperature of reaction is not particularly limited, can carries out the scope of 0 DEG C ~ 300 DEG C.About the reaction times, the arbitrary reaction times can be set, such as, infrared spectrometer can be utilized to follow the trail of the remaining quantity of isothiocyanate group, stopped reaction after reaching desired remaining quantity.
Carry out under reaction in the presence of a catalyst, does not exist.When using catalyzer, the catalyzer enumerated in above-mentioned [with the reaction of compound with hydroxyl] can be used in.
The reaction unit used when implementing reaction is not particularly limited, known reactor can be used.As reaction unit, such as can by appropriately combined uses of existing known reactor such as steel basin, adding pressure type steel basin, decompression type steel basin, tower reactor, distillation tower, packed tower, film distillators.The material of reactor is also not particularly limited, known material can be used.As the material of reactor, such as, can use glass system, stainless steel, carbon steel system, Hastelloy system or the material of glass lining is imposed to base material or has carried out the material that Teflon (registered trademark) is coated with.The cost of SUS304, SUS316, SUS316L etc. is low, can preferably use.As required, can the known process unit such as the instrument such as additional flow meter, thermometer, reboiler, pump, condenser, heating can utilize the known method such as steam, well heater to carry out, and cooling also can use the known methods such as naturally cooling, water coolant, secondary refrigerant.Can also additional process as required.
Can by such method manufacture containing the resin combination of modification of resin comprising at least one structural unit be selected from group that the group represented by above-mentioned formula (6) ~ (8) forms, but according to the difference of reaction conditions, sometimes also target resin can be obtained.In this case, by implementing heat treated shown below further, also target resin can be produced.
Heat treated is preferably the scope of 100 DEG C ~ 300 DEG C, more preferably carry out the scope of 150 DEG C ~ 250 DEG C.Heat treated can be carried out under air, also can carry out under inert gas atmosphere, preferably implement under inert gas atmosphere.Said rare gas element refers to the gases such as nitrogen, helium, argon, neon herein.In addition, pressure can be pressurization, decompression or normal atmosphere.The time of carrying out heat treated is not particularly limited, can carry out with the scope of 1 minute ~ 500 hours, infrared spectrometer such as can be used to follow the trail of the growing amount of the group represented by above-mentioned formula (6) ~ (8), after reaching desired amount, stop heating.
In above-mentioned manufacture method, think and generate group represented by above-mentioned formula (6) ~ (8) by various reaction path, such as infer the reaction generated based on following formula (111), the compound then generating the right in following formula (111) forms the reaction of ring structure by following formula (112) or formula (113).
(in formula, R 41and R 42for the group that above-mentioned formula (100) defines,
Y represents-NH-base or organic group,
Z represents Sauerstoffatom or sulphur atom.)
The resin combination of the modification of present embodiment can be used alone, and also preferably mixes with other resin.Other mixed resin can be any resin, can use known various resin.
The resin combination of the modification of present embodiment may be used in known various uses, and wherein, the purposes as class coating material that at least one material surface in the group selecting free metal, glass and plastics to form is formed is suitable.In addition, the resin combination of present embodiment is formed by the reaction of hydrostable functional group, is thus also preferred for aqueous coating.
The resin combination of the modification of present embodiment containing sulphur atom, thus improves effect with the adaptation of metallic surface and becomes large in molecular chain.Therefore, resin combination can be suitably used in the pre-coated metal comprising Rustproof Steel Plate, automobile coating etc. for giving aesthetic property, weathering resistance, acid resistance, rust-preventing characteristic, chipping resistance, adaptation etc.
<< oxazolidine thioketones >>
The preferred structure > of <
In present embodiment, preferred 2nd resin is the resin of the molecular chain comprised represented by following formula (10).
(in formula, P 1represent aliphatic group and/or aromatic group, Q 1represent the structural unit of more than a kind be selected from group that the divalent group represented by following formula (11), (12), (13) or (14) forms, the P of more than 2 1and Q 1can be the same or different, n represents the integer of more than 2.)
In formula, R 1represent aliphatic group or aromatic group, X 2and Y 2represent Sauerstoffatom or sulphur atom independently of one another, with R more than 2 in a part 1, X 2and Y 2can be the same or different respectively.A Q 1in X 2and Y 2in more than 1 be sulphur atom.In other words, Q1 comprises the sulphur atom of more than 1.
Surprisingly, the structure represented by above-mentioned formula (11) ~ (14) forming this resin adaptation, particularly with the adaptation of metallic surface in excellent.The principle playing this effect is still not clear, but the present inventor infers it may is because the sulphur atom comprised in this bonding or Sauerstoffatom play the effect improving adaptation.
Like this, the feature of the resin of present embodiment is the bonding pattern comprised in its molecule, and be not particularly limited the skeleton structure beyond this bonding, preferred mode is as follows.
The number-average molecular weight of resin is preferably more than 500, is more preferably more than 1000, more preferably more than 5000.In general, molecular weight is higher, then have the tendency that thermotolerance is better; On the other hand, when molecular weight is too high, sometimes be disadvantageous from the aspect of treatability (with the Combination, mobility, ductility etc. of other composition) when forming film, thus number-average molecular weight is preferably less than 1,000,000, is more preferably less than 500,000, more preferably less than 200,000.Said number-average molecular weight is the value calculated as follows herein: use that to possess at least 1 exclusion limit molecular weight be that the gel permeation chromatography of the post of more than 1,000 ten thousand measures, utilize the reference materials such as polystyrene, hold-time will be converted into molecular weight, calculate thus.Those skilled in the art easily can obtain number-average molecular weight.Calculate after except the peak from solvent.
The content contributing to the key of thermotolerance performance is also relevant with above-mentioned number-average molecular weight Mn.By the sulphur atom of the number-average molecular weight of resin divided by the formation nitrogen-carbon-sulfide linkage comprised in every 1 molecule and the quantity n of the Sauerstoffatom of formation nitrogen-carbon-oxygen bond 1and the value (Mn/n obtained 1) be preferably less than 300, be more preferably less than 200, more preferably less than 150.As mentioned above, the resin combination of present embodiment with the adaptation of metal in also can have effect, from the viewpoint of showing this effect, also preferably there is more above-mentioned key in every 1 molecule resin.On the other hand, when resin has too much above-mentioned key, particularly resin have above-mentioned formula (6) ~ (8), (11) ~ (14), (41), (42), (45), (46) or the structural unit represented by (47) time, the flexibility as one of film performance sometimes also can be impaired.From the viewpoint of this, Mn/n 1be preferably more than 50, be more preferably more than 70.N 1such as can calculate as follows: such as by infrared absorption spectrum or 1h-NMR etc. obtain the quantity X of this key of per unit weight (1g) resin 1(unit mol/g), according to formula: n 1=MnX 1calculated by above-mentioned number-average molecular weight (Mn).When resin comprises nitrogen-carbon-sulfide linkage and nitrogen-carbon-oxygen bond, n 1form the sulphur atom of each key and the sum of Sauerstoffatom.
R in above-mentioned formula (11) ~ (14) 1for aliphatic group or aromatic group.Alkyl has more than at least a kind in aliphatic group, aromatic group, except carbon atom, also can have Sauerstoffatom, nitrogen-atoms etc.The preferred carbonatoms of aliphatic group is the aliphatic group of 1 ~ 22, and more preferably carbonatoms is the aliphatic group of 1 ~ 18.The preferred carbonatoms of aromatic group is the aromatic group of 6 ~ 22, and more preferably carbonatoms is the aromatic group of 6 ~ 15.Also preferably carbonatoms be 1 ~ 5 aliphatic group and carbonatoms be the carbonatoms of the aromatic group bonding of 6 ~ 15 be the group of 7 ~ 20.
R 1concrete example can enumerate the straight-chain alkyls such as methylene radical, dimethylene, trimethylene, tetramethylene, pentamethylene, hexa-methylene, eight methylene radical; Pentamethylene, hexanaphthene, suberane, cyclooctane, two (cyclohexyl) paraffinic hydrocarbons etc. are without the group in the ester ring type hydrocarbon source replaced; The group in the alkyl substituted cyclohexane sources such as methylcyclopentane, ethyl cyclopentane, methylcyclohexane (Isomers), ethylcyclohexane (Isomers), propyl cyclohexane (Isomers), butyl cyclohexane (Isomers), pentylcyclohexane (Isomers), hexyl hexanaphthene (Isomers); The group in the dialkyl group substituted cyclohexane sources such as dimethyl cyclohexane (Isomers), diethyl cyclohexane (Isomers), dibutyl hexanaphthene (Isomers); The group in the trialkyl substituted cyclohexane such as 1,5,5-trimethyl-cyclohexane, 1,5,5-triethyl hexanaphthene, 1,5,5-tripropyl hexanaphthene (Isomers), 1,5,5-tributyl hexanaphthene (Isomers) source; The monoalkyl substituted benzenes such as toluene, ethylbenzene, propyl benzene; Dimethylbenzene, diethylbenzene, dipropyl benzene etc. are dialkyl substituted; The group etc. in the aromatic hydrocarbons sources such as phenylbenzene paraffinic hydrocarbons, benzene.
Among these, the group in preferred hexane, benzene, ditan, toluene, hexanaphthene, dimethylbenzene, methylcyclohexane, isophorone or dicyclohexyl methyl hydride source." group in source " represents the group of the structure from this compound after removing 2 hydrogen atoms.
Or, R 1preferably carbonatoms is aliphatic group, the carbonatoms of 1 ~ 25 is the aromatic group of 6 ~ 25.R 1be preferably the group not containing volution atom.R 1concrete example be remove the residue after 2 hydrogen atoms from methane, ethane, propane, butane, pentane, hexane, octane, decane, dodecane, octadecane, hexanaphthene, cyclooctane, dimethyl cyclohexane, diethyl cyclohexane, trimethyl-cyclohexane, trimethylethyl hexanaphthene, dicyclohexyl methyl hydride, tetramethyl-dicyclohexyl methyl hydride, benzene,toluene,xylene, ethylbenzene, diethylbenzene, ditan, tetramethyl-ditan etc.When there is isomer, also comprise this isomer.
Among these, R 1be preferably the divalent group represented by following formula (301) ~ (306).
(in formula, i represents the integer of 1 ~ 12, can be 1 ~ 10.)
In above-mentioned formula (10), P 1for aliphatic group and/or aromatic group.P 1except there is carbon atom, also Sauerstoffatom, nitrogen-atoms etc. can be had.
P in above-mentioned formula (10) 1more preferably ehter bond or ester bond is comprised, the group more preferably represented by following formula (114).
(in formula, R 43represent aliphatic group or aromatic group,
B 2represent the integer of 1 ~ 3.With R more than 2 in a part 43and b 2can be the same or different respectively.)
In above-mentioned formula (114), R 43for aliphatic group or aromatic group.R 43except there is carbon atom, also Sauerstoffatom, nitrogen-atoms etc. can be had.Aliphatic group can be ring type, also can be acyclic formula.The preferred carbonatoms of aliphatic group is the aliphatic group of 1 ~ 22, and more preferably carbonatoms is the aliphatic group of 1 ~ 18.The preferred carbonatoms of aromatic group is the aromatic group of 6 ~ 22, and more preferably carbonatoms is the aromatic group of 6 ~ 15.Also preferably have carbonatoms be 1 ~ 5 aliphatic group and carbonatoms bonded thereto be the carbonatoms of the aromatic group of 6 ~ 15 be the group of 7 ~ 20.
As the R in above-mentioned formula (114) 43preferred concrete structure, the group represented by following formula (115) can be enumerated.
(in formula, R 44represent the group of more than a kind be selected from the group be made up of hydrogen atom, chlorine atom, bromine atoms, fluorine atom and methyl,
R 45represent the group be selected from group that the group represented by following formula (116), (117), (118) or (119) forms,
The R of more than 2 44can be the same or different.)
More particularly, the P in above-mentioned formula (10) 1be preferably the group represented by following formula (201) ~ (204).
In above-mentioned formula (11) ~ (14), X 2and Y 2represent Sauerstoffatom or sulphur atom independently of one another, the X in a unit 2and Y 2it is asynchronously Sauerstoffatom.That is, the X in a unit 2and Y 2in at least one be sulphur atom.By comprising sulphur atom, with the adaptation of adherend, particularly improve with the adaptation of metallic surface.
The structure of the not shown end of structure represented by above-mentioned formula (10), but purport of the present invention is the improvement of the adaptation in epoxy resin and modified epoxy etc. in one aspect, as mentioned above, in compound of the present invention (as forming the atom of compound of the present invention) comprise sulphur atom and/or Sauerstoffatom is very important, think that the difference of end structure may not necessarily produce larger impact.In addition, as described later, the compound represented by above-mentioned formula (10) can be manufactured by the compound with terminal epoxy groups and the compound with end isothiocyanate group (-NCS), the compound with end-rings sulfenyl and the compound with terminal isocyanate group (-NCO) or end-rings sulfenyl and the compound combination with end isothiocyanate group.The difference of the compound used according to the compound in order to obtain above-mentioned formula (10), the structure of end can be epoxy group(ing), epithio base, isocyanate group or isothiocyanate group.In addition, as recorded in < manufacture method >, tripolymer is carried out to isocyanate group and the isocyanurate group (when different trithiocyanuric acid ester group for different trithiocyanuric acid ester group) that obtains also is contained in the compound of present embodiment sometimes.The N-originated by the reaction of the alcohol hydroxyl group in epoxy resin (aftermentioned) and isothiocyanate group replaces that-O-replaces thiocarbamate base, the N-that originated by the reaction of the thiol in episulfide resin (aftermentioned) and isocyanate group replaces that-S-replaces thiocarbamate base, the dithiocarbamate groups of being originated by the reaction of the thiol in episulfide resin and isothiocyanate group is also included sometimes.
< manufacture method >
The compound (resin) of present embodiment such as can be manufactured with the combination of the compound with end isothiocyanate group by the compound with terminal epoxy groups and the compound with end isothiocyanate group (-NCS), the compound with end-rings sulfenyl and the compound with terminal isocyanate group (-NCO) or the compound with end-rings sulfenyl.
The compound (resin) of present embodiment preferably by the compound (there is the compound of terminal isocyanate group, there is the compound of end isothiocyanate group) represented by following formula (31), with the reaction of the compound (there is the compound of terminal epoxy groups, there is the compound of end-rings sulfenyl) represented by following formula (20) and obtaining.
XCN——R 1-NCX(31)
(in formula, R 2represent aliphatic group or aromatic group,
R 1represent aliphatic group or aromatic group, X and Y 2represent Sauerstoffatom or sulphur atom independently of one another.)
The combination of the compound represented by formula (31) and the compound represented by formula (20) is compound and/or the Y of the formula (31) of sulphur atom according to X 2the mode comprising more than a kind for the compound of the formula (20) of sulphur atom is selected.
When respectively the compound represented by formula of more than two kinds (31), the compound combination represented by formula (20) being reacted, the R of more than 2 1and R 2can be the same or different.
In the compound represented by above-mentioned formula (20), there is the compound of compound (being also designated as epoxy resin) preferably represented by following formula (120) of terminal epoxy groups.
(in formula, R 2represent aliphatic group or aromatic group.)
As the concrete example of the compound represented by formula (120), can enumerate: the bisphenol-type epoxy resin bisphenols such as dihydroxyphenyl propane, Bisphenol F, dihydroxyphenyl propane D, bisphenol S, tetramethyl-dihydroxyphenyl propane, tetramethyl-Bisphenol F, tetramethyl-dihydroxyphenyl propane D, tetramethyl-bisphenol S, tetrabromo-bisphenol, tetrachlorobisphenol A, tetrafluoro dihydroxyphenyl propane being carried out to Glycidyl; Other dihydric phenols such as xenol, dihydroxy naphthlene, 9,9-two (4-hydroxy phenyl) fluorenes are carried out to the epoxy resin of Glycidyl; To 1,1, three phenols such as 1-tri-(4-hydroxy phenyl) methane, 4,4-(1-(4-(1-(4-hydroxy phenyl)-1-methylethyl) phenyl) ethylidene) bis-phenol carry out the epoxy resin of Glycidyl; Four phenols such as 1,1,2,2 ,-four (4-hydroxy phenyl) ethane are carried out to the epoxy resin of Glycidyl; The glycidyl ethers such as the phenolic resin varnish type epoxy resin of Glycidyl are carried out to phenolic varnish classes such as phenolic varnish, cresol novolak, bisphenol A novolac, brominated phenols Novolac, brominated bisphenol A phenolic varnish; The glycidyl esters classes such as the diglycidyl ester of hexahydrophthalic acid or dimeracid.These compounds with terminal epoxy groups can be used alone, and also can share two or more.
In compound represented by above-mentioned formula (20), there is the compound of compound (being also designated as episulfide resin) preferably represented by following formula (121) of end-rings sulfenyl.
(in formula, R 2represent aliphatic group or aromatic group.)
As the concrete example of the compound represented by formula (121), the bisphenol type episulfide resin bisphenols such as dihydroxyphenyl propane, Bisphenol F, dihydroxyphenyl propane D, bisphenol S, tetramethyl-dihydroxyphenyl propane, tetramethyl-Bisphenol F, tetramethyl-dihydroxyphenyl propane D, tetramethyl-bisphenol S, tetrabromo-bisphenol, tetrachlorobisphenol A, tetrafluoro dihydroxyphenyl propane being carried out to sulfo-Glycidyl can be enumerated; Other dihydric phenols such as xenol, dihydroxy naphthlene, 9,9-two (4-hydroxy phenyl) fluorenes are carried out to the episulfide resin of sulfo-Glycidyl; To 1,1, three phenols such as 1-tri-(4-hydroxy phenyl) methane, 4,4-(1-(4-(1-(4-hydroxy phenyl)-1-methylethyl) phenyl) ethylidene) bis-phenol carry out the episulfide resin of sulfo-Glycidyl; Four phenols such as 1,1,2,2 ,-four (4-hydroxy phenyl) ethane are carried out to the episulfide resin of sulfo-Glycidyl; The sulfo-glycidyl ethers such as the phenolic varnish type episulfide resin of sulfo-Glycidyl are carried out to phenolic varnish classes such as phenolic varnish, cresol novolak, bisphenol A novolac, brominated phenols Novolac, brominated bisphenol A phenolic varnish; The sulfo-glycidyl esters classes such as the dithioglycidol base ester of hexahydrophthalic acid or dimeracid.These compounds with end-rings sulfenyl can be used alone, and also can share two or more.
R in formula (31) 1preferably be selected from the alkyl in the group that the alkyl represented by following formula (301) ~ (306) forms.
(in formula, i represents the integer of 1 ~ 12, can be 1 ~ 10.)
In compound represented by above-mentioned formula (31), there is the compound of compound (isocyanate compound) preferably represented by following formula (122) of terminal isocyanate group.
O＝C＝N——R 1——N＝C＝O(122)
(in formula, R 1represent aliphatic group or aromatic group.)
As the concrete example of the compound represented by formula (122), tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 2 can be enumerated, 2,4-trimethylammonium-1,6-bis-isocyanato-hexane, lysinediisocyanate, isophorone diisocyanate, 1, two (the isocyanatomethyl)-hexanaphthene, 4 of 3-, 4 '-dicyclohexyl methane diisocyanate, 4,4 '-diphenylmethanediisocyanate, tolylene diisocyanate (Isomers), naphthalene diisocyanate (Isomers) etc.Compound represented by further preferred formula (122) to be carbonatoms be 4 ~ 20 aliphatic diisocyanate, carbonatoms be the alicyclic diisocyanate of 8 ~ 20.Among these, for the easiness that weathering resistance, heat-resisting yellow modification, industry obtain, preferred hexamethylene diisocyanate, isophorone diisocyanate.These isocyanate compounds can be used alone, and also can share two or more.
In compound represented by above-mentioned formula (31), there is the compound of compound (isothiocyanate compound) preferably represented by following formula (123) of end isothiocyanate group.
S＝C＝N——R 1——N＝C＝S(123)
(in formula, R 1represent aliphatic group or aromatic group.)
As the concrete example of the compound represented by formula (123), tetramethylene diisothio-cyanate can be enumerated, pentamethylene diisothio-cyanate, hexa-methylene diisothio-cyanate, 2, 2, 4-trimethylammonium-1, 6-diisothiocyanic acid root closes hexane, Methionin diisothio-cyanate, isophorone diisothio-cyanate, 1, two (isothiocyanato the methyl)-hexanaphthene of 3-, 4, 4 '-dicyclohexyl methyl hydride diisothio-cyanate, 4, 4 '-ditan diisothio-cyanate, toluene diisothio-cyanate (Isomers), naphthalene diisothio-cyanate (Isomers) etc.Compound represented by further preferred formula (123) to be carbonatoms be 4 ~ 20 aliphatic diisocyanate, carbonatoms be 8 ~ 20 alicyclic diisothio-cyanate.These compounds with end isothiocyanate group can be used alone, and also can share two or more.
Below, for the reaction of epoxy resin and isothiocyanate compound, the manufacture method of the compound of present embodiment is described.Also be same method when use episulfide resin replacement epoxy resin, the epoxy resin in following explanation can be replaced with episulfide resin, epoxy group(ing) be replaced with epithio base.In addition, the isothiocyanate compound in following explanation can be replaced with isocyanate compound, isothiocyanate group is replaced with isocyanate group when use isocyanate compound replacement isothiocyanate compound too.
About the consumption of isothiocyanate compound, preferably its isothiocyanate group uses with the amount reaching 20 ~ 60 equivalent % relative to epoxy group(ing).The consumption of isothiocyanate compound is more preferably 25 ~ 50 equivalent %, more preferably 30 ~ 47 equivalent %, is further preferably 30 ~ 45 equivalent %.Isocyanate group in isocyanate compound except being formed except ring structure with epoxy reaction, also for the alcohol hydroxyl group in epoxy resin formed thioxanthamide key or based on isothiocyanate group cyclisation 3 dimerization and form different trithiocyanuric acid ester ring.
Reaction is carried out usually in the presence of a catalyst.As catalyzer, such as butoxy lithium can be enumerated, the metal alcoholates such as sodium methoxide, lithium chloride, the mixture of the Lewis acids such as aluminum chloride and the Lewis base such as Lewis acid and triphenylphosphine oxide, tetramethyl-ammonium, tetraethyl ammonium, TBuA, the muriate of benzyl tributyl ammonium etc., bromide, iodide, the quaternary ammonium salt of acetic ester etc., triethylamine, N, N-dimethyl benzyl amine, 1, 8-diazabicyclo [5.4.0] 11 carbon-7-alkene, 1, the tertiary amines such as 4-diazabicyclo [2.2.2] octane, 2-ethyl-4-methylimidazole, the imidazoles etc. such as 2-phenylimidazole.These catalyzer can be used alone a kind or two or more is used in combination.As catalyzer, particularly preferably quaternary ammonium salt and tertiary amine.
The consumption of catalyzer uses in the scope of 5ppm ~ 2wt% relative to the gross weight of epoxy resin usually.The consumption of catalyzer is preferably 20ppm ~ 0.5wt%.Catalyzer also can be diluted in suitable solvent and use.
The manufacture method of present embodiment can be carried out under condition of no solvent, also can carry out under the existence of suitable solvent.
When using solvent, preferred use N, dinethylformamide, N, N-diethylformamide, METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO), N,N-DIMETHYLACETAMIDE, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), dimethylbenzene, toluene, methylcellosolve acetate, tetrahydrofuran (THF) etc. are not containing the solvent of active hydrogen.
Temperature of reaction is generally 80 DEG C ~ 300 DEG C.Be preferably 100 DEG C ~ 260 DEG C, more preferably 120 DEG C ~ 220 DEG C.If temperature of reaction is too low, the activity of catalyzer is low, can occur to generate the side reactions such as isocyanurate ring.In addition, the too high activity that catalyzer also can occur of temperature of reaction reduces, and side reaction is still carried out.
In the manufacture of the compound of present embodiment preferably, epoxy resin is warming up to specified temp, does one's utmost by being blown into dry air, nitrogen etc. to remove the moisture in resin, dropping into isothiocyanate compound and catalyzer afterwards.The input method of isothiocyanate compound and catalyzer can suitably be selected, and can disposablely drop into, and also can drop into several times, and also can drop into isothiocyanate compound continuously.Now, the input of lsothiocyanates and catalyzer can be carried out simultaneously, also can carry out respectively.When dropping into continuously, its making time is preferably 1 ~ 10 hour, is more preferably 2 ~ 5 hours.In short-term, the growing amount of different trithiocyanuric acid ester ring likely increases making time.
Epoxy group(ing) 20 ~ 45 equivalent % in the compound preferred epoxy of present embodiment (being preferably 22 ~ 42 equivalent %, more preferably 25 ~ 40 equivalent %) and the lsothiocyanates radical reaction in isothiocyanate compound; shape becomes oxazolidine-2-thioketones ring (be thiazoline-2-ketone ring in the reaction of episulfide resin and isocyanate compound, be thiazoline thioketones ring in the reaction of episulfide resin and isothiocyanate compound).
In epoxy group(ing) in the epoxy, the ratio of the epoxy group(ing) that ， is relevant to oxazolidine-2-thioketones ring such as can be obtained by following method: the method being measured Oxd rate by chemical gimmick; The gimmick of the equipment analysis such as infrared measure and nucleus magnetic resonance optical spectroscopy is utilized to carry out quantitative method.
Oxd rate is define Li as the equivalent % of the epoxy group(ing) of oxazolidine-2-thioketones ring relative to epoxy group(ing) originally.When epoxy group(ing) is not consumed in fact except the reaction of Xing Cheng oxazolidine-2-thioketones ring, utilize the epoxy equivalent (weight) (being called Ep1) of the epoxy resin used and weight (being called Wt1), the epoxy equivalent (weight) (being called Ep2) containing the epoxy resin of oxazolidine-2-thioketones ring obtained and weight (being called Wt2), obtain Oxd rate by following formula.
Oxd rate=100-(Wt2 ÷ Ep2) ÷ (Wt1 ÷ Ep1) × 100
The thioxanthamide key that the compound (resin) of present embodiment can obtain containing the reaction by the isothiocyanate group in part or all and isothiocyanate compound of the alcohol hydroxyl group in epoxy resin.Thioxanthamide key amount is preferably 0.9 equivalent/below kg, is more preferably 0.01 ~ 0.7 equivalent/kg, more preferably 0.05 ~ 0.6 equivalent/kg, is further preferably 0.1 ~ 0.5 equivalent/kg.
The compound (resin) of present embodiment can carry out the different trithiocyanuric acid ester ring of cyclisation 3 dimerization containing the isothiocyanate group in isothiocyanate compound.The content You Xuan of different trithiocyanuric acid ester ring Wei oxazolidine-2-thioketones ring content 40 below equivalent %, be more preferably 30 below equivalent %, more preferably 20 below equivalent %, be further preferably 10 below equivalent %.If different trithiocyanuric acid ester ring is too much, then when manufacturing, polymerization stability reduces sometimes.
The compound (resin) of present embodiment is not preferably in fact containing isocyanate group.
In order to improve mobility, the melt viscosity of the compound (resin) of present embodiment is preferably lower.Specifically, the melt viscosity of 125 DEG C is preferably below 8000mPas.Be more preferably below 6000mPas, more preferably below 4000mPas, be further preferably below 3000mPas.
The water-disintegrable chlorine dose of the compound (resin) of present embodiment is not particularly limited, such as, when Electrical and Electronic purposes uses, is preferably below 500ppm.Be more preferably below 100ppm.
When compound of the present invention (resin) has epoxy group(ing), properties-correcting agent can be utilized to carry out modification to part or all of epoxy group(ing).
As properties-correcting agent, be just not particularly limited with the compound of the functional group of epoxy reaction as long as have, the phenol such as such as xylenol, tert.-butyl phenol, nonylphenol, dihydroxyphenyl propane, quinhydrones can be enumerated; The alcohols such as propyl carbinol, ethylene glycol butyl ether, polyethyleneglycol ether, ethylene glycol, polypropylene glycol; The amines such as the dimethyl ketone imines of butylamine, octylame, diethylamine, methylbutylamine, monoethanolamine, diethanolamine, N-Mono Methyl Ethanol Amine, triethylamine hydrochloride, N, N-dimethylethanolamine acetate, amino ethyl ethanolamine; The carboxylic-acids such as acetic acid, lactic acid, 2 ethyl hexanoic acid, lauric acid, 12-oxystearic acid, phenylformic acid, dimethanol propionic acid; The thio-alcohols etc. such as diethyl disulfide acetate mixture sulfides class, γ-mercaptopropyi dimethoxymethylsilane, γ mercaptopropyitrimethoxy silane.
In addition, such as, also converting amino to ammonium salt etc. with the modified further use acetic acid of amine etc., the conversion to ionic group can be carried out.
[solidification compound]
The compound (resin) of present embodiment can mix with solidifying agent, thus for the preparation of solidification compound.
When solidification form is the solidification employing epoxy group(ing), as solidifying agent, the aliphatics amines such as such as quadrol, triethylene five amine, 1,6-hexanediamine, dimer acid modified quadrol, N-ethylamino piperazine can be enumerated; Mphenylenediamine, Ursol D, 3,3 '-diaminodiphenylsulfone(DDS), DDS, 4,4 '-diaminodiphenyl-methane, 4, the aromatic amines such as 4 '-diamino-diphenyl ether; The thio-alcohols such as the terminal sulfhydryl group compound of mercaptopropionic acid ester, epoxy resin; Dihydroxyphenyl propane, Bisphenol F, dihydroxyphenyl propane D, bisphenol S, tetramethyl-dihydroxyphenyl propane, tetramethyl-Bisphenol F, tetramethyl-dihydroxyphenyl propane D, tetramethyl-bisphenol S, tetrabromo-bisphenol, tetrachlorobisphenol A, tetrafluoro dihydroxyphenyl propane, xenol, dihydroxy naphthlene, 1,1, the resol classes such as 1-tri-(4-hydroxy phenyl) methane, 4,4-(1-(4-(1-(4-hydroxy phenyl)-1-methylethyl) phenyl) ethylidene) bis-phenol, phenolic varnish, cresol novolak, bisphenol A novolac, brominated phenols Novolac, brominated bisphenol A phenolic varnish; The anhydrides such as poly-nonane diacid acid anhydride, methyl tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, Tetra hydro Phthalic anhydride, trimellitic acid 1,2-anhydride, pyromellitic acid dianhydride; The imidazoles such as glyoxal ethyline, 2-ethyl-4-methylimidazole, 2-phenylimidazole; The hydrazine classes such as adipic dihydrazide; The tertiary amines such as dimethyl benzyl amine, 1,8-diazabicyclo [5.4.0] 11 carbon-7-alkene; Dyhard RU 100 etc.In addition, these solidifying agent can be used alone, and also can share two or more.
When solidification form is the solidification of the secondary hydroxyl employing the crosslinkable groups introduced by the modification of epoxy group(ing) or generated by modification, as solidifying agent, such as, use melamine resin, polyisocyanate compound, blocked isocyanate compounds etc.In addition, these solidifying agent can be used alone, and also can share two or more.
As melamine resin, hexa methoxy melamine methylol, methyl-butvl trimeric cyanamide, butylated melamines etc. can be exemplified.In addition, these melamine resins can be used alone, and also can share two or more.
As polyisocyanate compound, tetramethylene diisocyanate can be exemplified, pentamethylene diisocyanate, HDI, 2, 2, 4 (or 2, 4, 4)-trimethylammonium-1, 6-bis-isocyanato-hexane, lysinediisocyanate, isophorone diisocyanate, 1, two (the isocyanatomethyl)-hexanaphthene of 3-, 4, 4 '-dicyclohexyl methane diisocyanate, tetramethylxylene diisocyanate, tolylene diisocyanate, 4, 4 '-diphenylmethanediisocyanate, 1, 5-naphthalene diisocyanate, tolidine diisocyanate, xylylene diisocyanate, the vulcabond such as norcamphane vulcabond and the polyisocyanates derived by these vulcabond.These polyisocyanates can be used alone, and also can share two or more.
As the polyisocyanates derived by vulcabond, comprise isocyanuric acid ester type polyisocyanates, biuret form polyisocyanates, carbamate types polyisocyanates, allophanic acid ester type polyisocyanates etc.These polyisocyanate compounds can be used alone, and also can share two or more.
As blocked isocyanate compounds, use the compound above-mentioned vulcabond and/or polyisocyanate compound closed by end-capping reagent.
As end-capping reagent, such as alcohols, phenols, oximes, lactams, active methylene group class etc. can be enumerated.These end-capping reagents can be used alone, and also can share two or more.
About the consumption of solidifying agent, relative to the total amount of compound comprising present embodiment, can select arbitrarily, be generally 0.1 ~ 90 % by weight.The consumption of solidifying agent is preferably 0.1 ~ 50 % by weight.
Solidification compound can comprise solvent as required.As solvent, can according to object and purposes from hydro carbons such as such as benzene,toluene,xylene, hexanaphthene, mineral essential oil, petroleum naphthas; The ketones such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK); The ester classes such as ethyl acetate, n-butyl acetate, propylene glycol methyl ether acetate; The alcohols such as methyl alcohol, Virahol, propyl carbinol, ethylene glycol butyl ether, diethylene glycol monobutyl ether; Suitable choice for use in the groups such as water.These solvents can be used alone, and also can share two or more.
Solidification compound can comprise curing catalyst as required.As curing catalyst, use the metal catalyst classes etc. such as such as imidazoles, tertiary amines, phosphine class, aminotriazole class, tin system, zinc system.These curing catalysts can be used alone, and also can share two or more.
In solidification compound, pigment, weighting agent, additive etc. conventional in this technical field shown below can be used.Such as quinacridone can be enumerated, azo system, the pigment dyestuffs such as phthalocyanine system, titanium dioxide, metal foil-like pigment, the mineral dyes such as rust-stabilising pigment, barium sulfate, calcium carbonate, silicon-dioxide, carbon black, talcum, the weighting agents such as clay, hindered amine system, benzotriazole system, the UV light absorber such as benzophenone series, hindered phenol system, phosphorus system, sulphur system, the antioxidants such as hydrazides system, silane system, the coupling agents such as titanium system, flow agent, rheology control agent, pigment dispersing agent, anticrater agent, the additives etc. such as defoamer.In addition, as required, the strongtheners such as glass fibre, woven fiber glass, carbon fiber can be contained.
The solidification compound of present embodiment has excellent adaptation and good mobility concurrently, is suitable as the materials such as coating, joint compound, sealing material, formed material, matrix material, laminated board, packaged material such as powder coating, electrocoating paint, PCM coating.
<< has the resin >> of different trithiocyanuric acid ester structure
The preferred structure > of <
In present embodiment, preferred 3rd resin has the structural unit represented by more than 2 following formula (40).This resin has the structural unit of more than a kind in the group that 1 valency, divalent or the 3 valency groups that are selected from represented by following formula (41) ~ (47) form further.R in structural unit represented by formula (41) ~ (47) 3can with isothiocyanate group Direct Bonding, form the structural unit of formula (40).N in 1 structural unit represented by formula (41) ~ (47) not with the N Direct Bonding in other structural unit represented by formula (41) ~ (47).
SCN——R 3——(40)
(in formula, R 3represent organic group, R 4represent aliphatic group or aromatic group, X 3represent Sauerstoffatom or sulphur atom.With R more than 2 in a part 3, R 4and X 3can be the same or different.R 3can be aliphatic group or aromatic group.)
Usually, the in fact all nitrogen-atoms forming this polyisothiocyanates are combined with at least 1 carbon atom.That is, each structural unit is not by N Direct Bonding each other.In addition, the R in each structural unit 3can with isothiocyanate group Direct Bonding, form the structural unit represented by formula (40).Such as, the structural unit represented by through type (41) and isothiocyanate group bonding, can form the mono-functional's repeating unit represented by formula (46) or two functionality repeating units represented by formula (47).Polyisothiocyanates can have not with R 3the isothiocyanate group of bonding.
To-the X comprised in formula (43) and (45) 3-R 4represented functional group is described.
In the manufacture method of polyisothiocyanates described later, manufacture has the N represented by formula (43), when N '-two replaces the polyisothiocyanates of dithio allophanic acid key or the replacement of the N-represented by formula (45)-O-replacement thiocarbamate base or N-replacement-S-replacement dithiocarbamate groups, use oxy-compound, thio-alcohol.-X 3-R 4represented functional group is the group from this oxy-compound or thio-alcohol, when using oxy-compound, and X 3for Sauerstoffatom, when using thio-alcohol, X 3for sulphur atom.
About the R in formula (40) ~ (47) 3, as aliphatic group, preferred carbonatoms is the aliphatic group of 1 ~ 22, and more preferably carbonatoms is the aliphatic group of 1 ~ 18.As aromatic group, preferred carbonatoms is the aromatic group of 6 ~ 22, and more preferably carbonatoms is the aromatic group of 6 ~ 15.Also preferably to have carbonatoms be the aliphatic group of 1 ~ 5 and be the group of 7 ~ 20 with the carbonatoms that the carbonatoms of this aliphatic group bonding is the aromatic group of 6 ~ 15.
Among these, R 3be preferably the divalent group represented by following formula (301) ~ (306).
(in formula, i represents the integer of 1 ~ 12, can be 1 ~ 10.)
As R 4concrete example, methyl can be enumerated, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, dodecyl, octadecyl, cyclopentyl, cyclohexyl, suberyl, ring octyl group, methylcyclopentyl, ethylcyclopentyl, methylcyclohexyl, ethylcyclohexyl, propylcyclohexyl, butylcyclohexyl, pentylcyclohexyl, hexyl cyclohexyl, Dimethylcyclohexyl, diethyl cyclohexyl, dibutyl cyclohexyl, phenyl, aminomethyl phenyl, ethylphenyl, propyl group phenyl, butyl phenyl, amyl group phenyl, hexyl phenyl, octyl phenyl, nonyl phenyl, cumyl phenyl, 3,5-dimethylphenyl etc.
Surprisingly, the thermotolerance forming the structural unit represented by above-mentioned formula (41) ~ (47) of this resin is high, adaptation, particularly with the excellent adhesion of metallic surface.Be still not clear about the principle that can play this effect, the present inventor infer may be due to, can improve thermotolerance when having 6 stable ring structure, the sulphur atom comprised in this bonding can play and improve the effect of adaptation.
Like this, the feature of the resin of present embodiment is the bonding pattern comprised in its molecule, and be not particularly limited the skeleton structure beyond this bonding, preferred mode is as follows.
The number-average molecular weight of resin is preferably more than 500, is more preferably more than 1000, more preferably more than 5000.In general, molecular weight is higher, then have the tendency that thermotolerance is better; On the other hand, when molecular weight is too high, sometimes be disadvantageous from the aspect of treatability (with the Combination, mobility, ductility etc. of other composition) when forming film, thus number-average molecular weight is preferably less than 1,000,000, is more preferably less than 500,000, more preferably less than 200,000.Said number-average molecular weight is the value calculated as follows herein: use that to possess at least 1 exclusion limit molecular weight be that the gel permeation chromatography of the post of more than 1,000 ten thousand measures, utilize the reference materials such as polystyrene, hold-time will be converted into molecular weight, calculate thus.Those skilled in the art easily can obtain number-average molecular weight.Calculate after except the peak from solvent.
The content contributing to the key of thermotolerance performance is also relevant with above-mentioned number-average molecular weight Mn.By the sulphur atom of the number-average molecular weight of resin divided by the formation nitrogen-carbon-sulfide linkage comprised in every 1 molecule and the quantity n of the Sauerstoffatom of formation nitrogen-carbon-oxygen bond 1and the value (Mn/n obtained 1) be preferably less than 300, be more preferably less than 200, more preferably less than 150.As mentioned above, the resin combination of present embodiment with the adaptation of metal in also can have effect, from the viewpoint of showing this effect, also preferably there is more above-mentioned key in every 1 molecule resin.On the other hand, when resin has too much above-mentioned key, particularly resin have above-mentioned formula (6) ~ (8), (11) ~ (14), (41), (42), (45), (46) or the structural unit represented by (47) time, the flexibility as one of film performance sometimes also can be impaired.From the viewpoint of this, Mn/n 1be preferably more than 50, be more preferably more than 70.N 1such as can calculate as follows: such as by infrared absorption spectrum or 1h-NMR etc. obtain the quantity X of this key of per unit weight (1g) resin 1(unit mol/g), according to formula: n 1=MnX 1calculated by above-mentioned number-average molecular weight (Mn).When resin comprises nitrogen-carbon-sulfide linkage and nitrogen-carbon-oxygen bond, n 1form the sulphur atom of each key and the sum of Sauerstoffatom.
The preferred manufacture method > of <
The resin that the resin of present embodiment preferably makes to have the compound of nitrogen-carbon-sulfide linkage and polyisothiocyanates reaction and obtains.Nitrogen-carbon-sulfide linkage is made up of nitrogen-atoms, carbon atom and sulphur atom, these atoms bonding successively.
In addition, the resin of present embodiment is preferably through comprising the resin method of the step of the compound polymerization represented by following formula (33) obtained.
SCN——R 3——NCS(30)
(in formula, R 3representing organic group, can be aliphatic group or aromatic group.)
In above-mentioned formula (30), R 3represent aliphatic group, aromatic group or the group (aliphatic group with aromatic group replaces) be combined to form by them.The compound of formula (30) used as the monomer of polymerization can be R 3the combination of different compounds of more than two kinds.Except carbon atom, as R 3aliphatic group and aromatic group also can have Sauerstoffatom, nitrogen-atoms etc.As aliphatic group, preferred carbonatoms is the aliphatic group of 1 ~ 22, and more preferably carbonatoms is the aliphatic group of 1 ~ 18.The preferred carbonatoms of aromatic group is the aromatic group of 6 ~ 22, and more preferably carbonatoms is the aromatic group of 6 ~ 15.Also preferably to have carbonatoms be the aliphatic group of 1 ~ 5 and be the group of 7 ~ 20 with the carbonatoms that the carbonatoms of this aliphatic group bonding is the aromatic group of 6 ~ 15.
As R 3concrete example, the straight-chain alkyls such as methylene radical, dimethylene, trimethylene, tetramethylene, pentamethylene, hexa-methylene, eight methylene radical can be enumerated; Pentamethylene, hexanaphthene, suberane, cyclooctane, two (cyclohexyl) methane etc. are without the group in the ester ring type hydrocarbon source replaced; The group in the alkyl substituted cyclohexane sources such as methylcyclopentane, ethyl cyclopentane, methylcyclohexane (Isomers), ethylcyclohexane (Isomers), propyl cyclohexane (Isomers), butyl cyclohexane (Isomers), pentylcyclohexane (Isomers), hexyl hexanaphthene (Isomers); The group in the dialkyl group substituted cyclohexane sources such as dimethyl cyclohexane (Isomers), diethyl cyclohexane (Isomers), dibutyl hexanaphthene (Isomers); The group in the trialkyl substituted cyclohexane such as 1,5,5-trimethyl-cyclohexane, 1,5,5-triethyl hexanaphthene, 1,5,5-tripropyl hexanaphthene (Isomers), 1,5,5-tributyl hexanaphthene (Isomers) source; The monoalkyl substituted benzenes such as toluene, ethylbenzene, propyl benzene; Dimethylbenzene, diethylbenzene, dipropyl benzene etc. are dialkyl substituted; The group etc. in the aromatic hydrocarbons sources such as benzene.
Among these, be preferably selected from the group of more than a kind in the group be made up of the group in hexane, benzene, ditan, toluene, hexanaphthene, dimethylbenzene, methylcyclohexane, isophorone or dicyclohexyl methyl hydride source." group in source " represents the group of the structure from this compound after removing 2 hydrogen atoms.
R in above-mentioned formula (30) 3be more preferably the group represented by following formula (301) ~ (306).
(in formula, i represents the integer of 1 ~ 12, can be 1 ~ 10.)
As the lsothiocyanates represented by above-mentioned formula (30), preferably can enumerate hexa-methylene diisothio-cyanate, isophorone diisothio-cyanate, 4 further, 4 '-dicyclohexyl methyl hydride diisothio-cyanate, 4,4 '-ditan diisothio-cyanate, toluene diisothio-cyanate (Isomers), naphthalene diisothio-cyanate (Isomers) etc.
Then, the manufacture method of the resin (polyisothiocyanates) of present embodiment is described.
The polyisothiocyanates of present embodiment such as can obtain by making the homopolymerization of monomer diisothio-cyanate.The polymerization of monomer diisothio-cyanate is preferably carried out under the existence of the catalyzer such as different trithiocyanuric acid esterifying catalyst described later.In addition, when by monomer diisothiocyanic acid polyisocyanate polyaddition, also oxy-compound or thio-alcohol can be used as auxiliary material, by the reaction of diisothio-cyanate and oxy-compound or thio-alcohol, urethane, allophanatization etc. are carried out to a part for isothiocyanate group, obtain polyisothiocyanates thus.
Monomer diisothio-cyanate refers to the compound represented by above-mentioned formula (33).
As oxy-compound, methyl alcohol can be enumerated, ethanol, propyl alcohol, butanols, amylalcohol, hexanol, enanthol, octanol, decyl alcohol, dodecanol, cyclopentanol, hexalin, suberyl alcohol, Lotka-Volterra circle system, methylcyclopentanol, ethyl cyclopentanol, methyl-cyclohexanol, ethyl cyclohexanol, cyclohexyl alcohol, butylcyclohexyl alcohol, amyl group hexalin, hexyl hexalin, dimethyl cyclohexanol, diethyl hexalin, dibutyl hexalin, phenol, methylphenol, ethylphenol, propylphenol, butylphenol, amyl phenol, hexylphenol, octyl phenol, nonylphenol, cumyl phenol, xylenol, methylethyl phenol, methyl-propyl phenol, methyl butyl phenol, methyl amyl phenol, diethyl phenol, ethyl propyl phenol, ethyl-butyl phenol, dipropyl phenol, dicumyl phenol, pseudocuminol, triethyl phenol, naphthols etc.In addition, also spent glycol, 1,2-PD or 1,3-PD, 1 can be made, 3-butyleneglycol, 1,4-butyleneglycol or 2,3-butanediol, 1,6-hexylene glycol, neopentyl glycol, neopentyl glycol hydroxypivalic acid ester, 2-ethyl-1,3-hexylene glycol, TriMethylolPropane(TMP), glycerine, 1, the polyester polyol, polyether glycol etc. of the low-molecular weight compounds such as 2,6-hexanetriol and number-average molecular weight about 200 ~ 10,000.
As thio-alcohol, thiomethyl alcohol can be enumerated, sulfur alcohol, propylmercaptan, butyl sulfhydryl, pentan-thiol, hexylmercaptan, heptanthiol, spicy thioalcohol, decyl mercaptan, Dodecyl Mercaptan, cyclopentyl mercaptan, cyclohexylmercaptan, ring heptanthiol, cyclooctasulfur alcohol, methyl cyclopentyl mercaptan, ethyl cyclopentyl mercaptan, methyl cyclohexane mercaptan, cyclohexyl mercaptan, cyclohexyl mercaptan, butylcyclohexyl mercaptan, amyl group cyclohexylmercaptan, hexyl cyclohexylmercaptan, dimethyleyelohexane mercaptan, diethyl cyclohexylmercaptan, dibutyl cyclohexylmercaptan, thiophenol, methylbenzene phenyl-sulfhydrate, ethyl thiophenol, propylbenzene thiophenol, butylbenzene thiophenol, amylbenzene thiophenol, hexyl benzene thiophenol, octyl group thiophenol, nonyl benzene thiophenol, cumyl thiophenol, thiophenol dimethyl benzene, methylethyl thiophenol, methyl-propyl thiophenol, methyl butyl thiophenol, methyl amyl thiophenol, diethylbenzene thiophenol, ethyl propyl thiophenol, ethyl-butyl thiophenol, dipropyl thiophenol, dicumyl thiophenol, trimethylbenzenethiol, triethylbenzene thiophenol, thionaphthol etc.
When using oxy-compound, the isothiocyanate group/hydroxyl equivalent of above-mentioned oxy-compound and monomer diisothio-cyanate is than selecting from the value of about 10 ~ 100 according to object.During use thio-alcohol too, isothiocyanate group/thiol equivalence ratio can be selected from the value of about 10 ~ 100 according to object.
As the different trithiocyanuric acid esterifying catalyst for the formation of the different trithiocyanuric acid ester group represented by above-mentioned formula (41), (46) or (47), be preferably quaternary ammonium salt, be more preferably quaternary ammonium hydroxide, quaternary ammonium carboxylic acid, further preferred quaternary ammonium carboxylic acid.
As the concrete example of different trithiocyanuric acid esterifying catalyst, the tetra-alkyl ammonium hydroxides such as Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TBAH can be enumerated; The organic monoacid salt etc. such as acetic acid tetramethyl ammonium, acetic acid tetraethyl-ammonium salt, tetrabutylphosphoniuacetate acetate ammonium salt.Also the metal-salt etc. of the alkyl carboxylic acid such as acetic acid, valeric acid, isovaleric acid, caproic acid, sad, TETRADECONIC ACID can be used, from the viewpoint of reducing consumption, preferred organic salt of weak acid etc.
Above-mentioned different trithiocyanuric acid esterifying catalyst can dilute rear use.As thinner, oxy-compound can be used.As oxy-compound, such as methyl alcohol, ethanol, n-butyl alcohol or 2-butanols, 2-methyl isophthalic acid-propyl alcohol, 1 can be enumerated, 2-propylene glycol or 1, ammediol, 1,3-butyleneglycol, 1, the phenolic hydroxyl group compounds such as alcohol hydroxyl group compound, phenol, cresols, xylenol, pseudocuminol such as 4-butyleneglycol or 2,3-butanediol, glycerine, hexalin.From the crystalline aspect of the polyisocyanates obtained thus, preferred 2-butanols, 2-methyl isophthalic acid-propyl alcohol, 1,3 butylene glycol or 2,3-butanediol etc. have the alcohol of side chain.In addition, also can mix two or more.Thio-alcohol can be used to replace this oxy-compound.
Make above-mentioned monomer diisothio-cyanate separately or isothiocyanate compound monomer diisothio-cyanate oxy-compound having been carried out urethane reacts under the existence of above-mentioned different trithiocyanuric acid esterifying catalyst time, carry out according to the condition being 1 ~ 20 quality % by the concentration of the different trithiocyanuric acid esterifying catalyst after above-mentioned oxy-compound dilution.Above-mentioned concentration is preferably 1 ~ 10 quality %.If concentration is more than 1 quality %, the amount of the oxy-compound accompanied with different trithiocyanuric acid esterifying catalyst can not become too much, and the polyisothiocyanates obtained and the physical property of film formed thus are difficult to reduce.If concentration is below 20 quality %, the co catalysis effect of the oxy-compound accompanied can not reduce, its result, is difficult to the increase of consumption, the painted of polyisothiocyanates etc. that cause different trithiocyanuric acid esterifying catalyst.
Except different trithiocyanuric acid esterifying catalyst, because of the acidic component that contains of trace in the raw materials such as monomer diisothio-cyanate, except the situation of inactivation, the consumption of different trithiocyanuric acid esterifying catalyst is 1ppm ~ 10% relative to the weight of monomer diisothio-cyanate, is preferably 10ppm ~ 5%.If amount more than the 1ppm of catalyzer, then can give full play to the function as different trithiocyanuric acid esterifying catalyst.If the amount of catalyzer less than 3%, then can cut down the addition of the reaction terminating agent (aftermentioned) such as acid phosphatase compound, acid phosphoesterase compound for making different trithiocyanuric acid esterifying catalyst inactivation.
Can use during reaction or not use solvent, but by using the solvent with isothiocyanate group without reactive behavior, the control of reaction becomes and is more prone to.
As the example of solvent, the esters such as ethyl acetate, butylacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate or ethers, benzene,toluene,xylene, ethylbenzene, trimethylbenzene etc. can be used aromatic hydrocarbon based.Certainly, also two or more solvent can be used.
Different trithiocyanuric acid esterification 30 DEG C ~ 120 DEG C, preferably carry out at 50 DEG C ~ 100 DEG C.The carrying out of reaction can by reaction solution 1h-NMR analyzes and confirms.When reaction reaches desired transformation efficiency, make catalyst deactivation by dropping into reaction terminating agent, thus stopped reaction.It is suitable that transformation efficiency is selected in the scope of 10 ~ 60%, is preferably 10 ~ 30%.During low conversion rate, the polyisothiocyanates that viscosity is lower can be obtained, but from the viewpoint of productivity, preferred transformation efficiency is more than 10%.On the other hand, if transformation efficiency is less than 60%, then the viscosity of polyisothiocyanates can not become too high, thus preferably.
Transformation efficiency can be obtained by following formula.About above-mentioned transformation efficiency, 1in H-NMR spectrogram, the peak of the methyl of tetramethylsilane is set to 0ppm, calculates transformation efficiency according to following formula by the integrated value (B) at the integrated value (A) at the peak of 3.5ppm and the peak of 4.8ppm.
Transformation efficiency (%)=B/ (A+B) × 100
As the reaction terminating agent of different trithiocyanuric acid esterification, use the compound of more than a kind be selected from the group be made up of acid phosphatase compound and acid phosphoesterase compound.
Acid phosphatase compound is mineral acid, can enumerate such as phosphoric acid, phosphorous acid, ortho phosphorous acid, diphosphorous acid, Hypophosporous Acid, 50, tetra-sodium, peroxide phosphoric acid etc.Be preferably phosphoric acid.
Acid phosphoesterase compound is the compound with acidic-group and ester group, can enumerate such as carbonatoms be 2 ~ 8 monoalkyl phosphoric acid esters, monoalkyl phosphorous acid ester, carbonatoms be 4 ~ 16 dialkyl phosphate, dialkyl phosphites, didodecyl phosphate, diphenyl phosphate, mono phosphoric acid ester lauryl, mono phosphoric acid ester phenyl ester, phosphorous acid two lauryl, diphenyl phosphite, phosphorous acid list lauryl, phosphorous acid monophenyl etc.Preferred carbonatoms be 3 ~ 8 monoalkyl phosphoric acid esters or carbonatoms be the dialkyl phosphate of 6 ~ 16, be more preferably dioctylphosphoric acid ester or mono-octyl phosphate.
Among these, preferably use acid phosphatase compound.The addition of acid phosphatase compound is preferably 1 ~ 10 equivalent relative to the stoichiometry of different trithiocyanuric acid esterifying catalyst, is more preferably 1 ~ 6 equivalent.If more than addition 1 equivalent, the abundant inactivation of different trithiocyanuric acid esterifying catalyst can be made.If below addition 10 equivalent, the filtration of the insolubles produced also can not become difficulty, thus preferably.
When using acid phosphatase compound, the different trithiocyanuric acid esterifying catalyst of inactivation can form insolubles in many cases, can pass through to filter.By filtering with crossing, thus the phosphorus that the acid phosphatase compound in polyisothiocyanates can be made to originate is reduced to the degree only detecting denier.
When using acid phosphoesterase compound, acid phosphoric acid ester and be dissolved in polyisothiocyanates with the salt of different trithiocyanuric acid esterifying catalyst, is thus mixed in the modified polyisocyanate after eliminating monomer diisothio-cyanate sometimes.
From the aspect of the concentration of phosphorus in polyisothiocyanates, preferably use acid phosphatase compound.When using acid phosphatase compound, by keeping 30 ~ 120 minutes at 90 ~ 150 DEG C, preferably 100 ~ 120 DEG C after interpolation acid phosphatase compound, thus filtration time cripetura in filter progress, filterableness improves.
After obtaining polyisothiocyanates, acid phosphatase compound, acid phosphoesterase compound can be added, particularly can add acid phosphatase compound.
As mentioned above, after the different trithiocyanuric acid esterification of stopping, from reaction solution, remove unreacted monomer diisothio-cyanate and solvent, refine.As process for purification, can underpressure distillation, solvent extraction etc. be enumerated, generally can use film distillator.
The content of the monomer diisothio-cyanate in the polyisothiocyanates after refining can be set to preferred below 1.0 quality %, preferred below 0.5 quality %.The unreacted monomer diisothio-cyanate reclaimed can reuse.
Polyisothiocyanates also can be used in combination with organic solvent.In this situation, as organic solvent, preferably not there is the functional group with hydroxyl and isocyanic ester radical reaction.As such organic solvent, ester cpds, ketone compound, aromatics etc. can be used.
According to object, also can mix in polyisothiocyanates and promote the various additive such as curing catalyst, pigment, flow agent, antioxidant, UV light absorber, photostabilizer, softening agent, tensio-active agent of urethane reaction etc. and use.
Polyisothiocyanates effectively can utilize in two-pack type polyurethane coating, sealing material, joint compound, ink, coating agent, mold material, elastomerics, foam, plastic raw materials, fibre finish, single solution curing type polyisothiocyanates etc. widely field.
Embodiment
, illustrate the present invention based on embodiment below, but scope of the present invention being not limited to these examples.As long as no special record, then " part " or " % " in embodiment and comparative example is weight basis.
[analytical procedure]
(1) 1h-NMR analyzes
Weigh about 0.3g sample, add deuterochloroform (U.S., Aldrich society manufacture, 99.8%) about 0.7g and tetramethylsilane (Japan, Wako Pure Chemical Industries, Ltd. manufacture and light one-level) 0.05g Homogeneous phase mixing as internal standard material, using obtained solution as NMR analytic sample.Use this sample, the JNM-A400FT-NMR system manufactured by NEC (strain) society is analyzed.
It should be noted that, the transformation efficiency of isocyanate group during manufacture polyisocyanates utilizes following method to calculate.
? 1in H-NMR spectrogram, the signal of the methyl of tetramethylsilane is set to 0ppm, calculates transformation efficiency according to following formula by the integrated value (B) of the integrated value (A) of the signal of the 3.3ppm from monomeric diisocyanate and the signal from the 3.8ppm of isocyanurate structure.
Transformation efficiency (%)=B/ (A+B) × 100
In addition, the transformation efficiency of isothiocyanate group during manufacture polyisothiocyanates utilizes following method to calculate.
? 1in H-NMR spectrogram, the signal of the methyl of tetramethylsilane is set to 0ppm, calculates transformation efficiency according to the integrated value (A) of following formula by the signal of the 3.5ppm from monomer diisothio-cyanate and the integrated value (B) from the signal of the 4.8ppm of different trithiocyanuric acid ester structure.
Transformation efficiency (%)=B/ (A+B) × 100
(2) number-average molecular weight
Dong Caoshe is used to manufacture GPC-8020 as determinator, use tetrahydrofuran (THF) as developing solvent, use Dong Caoshe to manufacture TSKgelSuperH3000, SuperH2000, SuperH1000 as post, carry out gel osmoticing chromatogram analysis (gpc analysis).Using about 10mg sample dissolution in the tetrahydrofuran (THF) of 10mL as mensuration sample, injection rate is 10 μ L.Compared by the elution time of the polystyrene known with the molecular weight utilizing differential refraction rate detector to observe, obtain number-average molecular weight.
(3) Evaluation of Heat Tolerance method
Utilize TG-8120 (manufacture of RIGAKU society), thermal weight loss mensuration is carried out in a nitrogen atmosphere with the condition of sample 10mg, heat-up rate 10 DEG C/min, situation about reducing to 5% weight unconfirmed within 300 DEG C is designated as A, the situation confirming 5% weight minimizing within 300 DEG C is designated as B.
(4) film evaluation method
The adaptation evaluation of film is carried out as follows.The film being formed at aluminium sheet (long 10cm, wide 10cm, thick 5mm) cuts the square otch of 1mm, impregnated in acetone together with aluminium sheet, within 24 hours, whether " Invest, Then Investigate " film is remaining.Every 1 sample carries out 10 same tests, and situation remaining for more than 8 pieces films is designated as A, and situation is in addition designated as B.
(5) copper-stripping intensity
Copper-stripping intensity is determined according to JISC6481.Situation good for copper-stripping intensity is expressed as A, and the situation of difference is expressed as B.
[embodiment 1]
Drop into adipic dihydrazide and polyisocyanates (DURANATETPA-100, Asahi Chemical Corp manufacture), make the equivalence ratio of isocyanate group and hydrazide group be 1.0, mixing butylacetate, prepares the dispersion liquid that solids component is 10%.This dispersion liquid is stirred 12 hours at 120 DEG C.Gather a part of reaction solution, use 1h-NMR analyzes, and result disappears from the peak near the 3.3ppm of isocyanic ester.Utilize rotatory evaporator by after butylacetate distillation removing, carry out the evaluation of thermotolerance.Evaluation result lists in table 1.
[embodiment 2]
Hydrazine monohydrate 36g is dissolved in Virahol 1L, is cooled to 0 DEG C, stir and add hexa-methylene diisothio-cyanate 50g.By filtering, generated solid being reclaimed, utilizing 1h-NMR analyzes, and result is 4, the two thiosemicarbazide of 4 '-hexa-methylene.
For this 4, the two thiosemicarbazide of 4 '-hexa-methylene and polyisocyanates (DURANATETPA-100, Asahi Chemical Corp manufacture), carry out the method identical with embodiment 1, carry out the evaluation of thermotolerance.Evaluation result lists in table 1.
[embodiment 3]
Hydrazine monohydrate 36g is dissolved in Virahol 1L, is cooled to 0 DEG C, stir and add hexamethylene diisocyanate 50g.By filtering, generated solid being reclaimed, utilizing 1h-NMR analyzes, and result is 4, the two Urea,amino-of 4 '-hexa-methylene.
For this 4, the two Urea,amino-of 4 '-hexa-methylene and polyisocyanates (DURANATETPA-100, Asahi Chemical Corp manufacture), carry out the method identical with embodiment 1, carry out the evaluation of thermotolerance.Evaluation result lists in table 1.
[embodiment 4]
Hydrazine monohydrate 36g is dissolved in Virahol 1L, is cooled to 0 DEG C, stir and add methacrylic acid 2-isocyanic ester root conjunction ethyl ester 280g.By filtering, generated solid being reclaimed, utilizing 1h-NMR analyzes, and result is methacrylic acid (2-(Hydrazinecarboxamidederivatives) ethyl ester).
Next, this methacrylic acid (2-(Hydrazinecarboxamidederivatives) ethyl ester) 100g is dissolved in toluene 1L, adds methyl methacrylate 80g and Diisopropyl azodicarboxylate 0.5g, be heated to 80 DEG C.Gather reaction solution after 3 hours, utilize 1h-NMR analyzes, and the double bond that result forms methyl methacrylate disappears.Utilize rotatory evaporator to be removed by toluene distillation, obtain the polymkeric substance with amino urea groups.
For this polymkeric substance and polyisocyanates (DURANATETPA-100, Asahi Chemical Corp manufacture), carry out the method identical with embodiment 1, carry out the evaluation of thermotolerance.Evaluation result lists in table 1.
[embodiment 5 ~ 8]
Replace polyisocyanates and use hexamethylene diisocyanate, in addition, carrying out the method identical with embodiment 1, carry out the evaluation of thermotolerance.Evaluation result lists in table 1.
[embodiment 9]
Carry out the method identical with embodiment 4, manufacture methacrylic acid (2-(Hydrazinecarboxamidederivatives) ethyl ester).For this methacrylic acid (2-(Hydrazinecarboxamidederivatives) ethyl ester) and polyisocyanates (DURANATETPA-100, Asahi Chemical Corp manufacture), carry out the method identical with embodiment 1, carry out the evaluation of thermotolerance.Evaluation result lists in table 1.
[reference example 1]
Replace the adipic dihydrazide of embodiment 1 and use hexamethylene glycol, carrying out the method identical with embodiment 1 in addition, carry out the evaluation of thermotolerance.Evaluation result lists in table 1.
[reference example 2]
Replace the adipic dihydrazide of embodiment 1 and use 1,6-hexanediamine, carrying out the method identical with embodiment 1 in addition, carry out the evaluation of thermotolerance.Evaluation result lists in table 1.
[reference example 3]
Methacrylic acid (2-hydroxy methacrylate) 100g is dissolved in toluene 1L, adds methyl methacrylate 80g and Diisopropyl azodicarboxylate 0.5g, be heated to 80 DEG C.Gather reaction solution after 3 hours, utilize 1h-NMR analyzes, and the double bond that result forms methyl methacrylate disappears.Utilize rotatory evaporator to be removed by toluene distillation, obtain the polymkeric substance with hydroxyl.For this polymkeric substance and polyisocyanates (DURANATETPA-100, Asahi Chemical Corp manufacture), carry out the method identical with embodiment 1, carry out the evaluation of thermotolerance.Evaluation result lists in table 1.
[reference example 4 ~ 6]
Replace the polyisocyanates of comparative example 1 and use hexamethylene diisocyanate, carrying out the method identical with embodiment 1 in addition, carry out the evaluation of thermotolerance.Evaluation result lists in table 1.
[reference example 7]
Replace the adipic dihydrazide of embodiment 1 and use methacrylic acid (2-hydroxyethyl) ester, carrying out the method identical with embodiment 1 in addition, carry out the evaluation of thermotolerance.Evaluation result lists in table 1.
[table 1]
The manufacture of [Production Example 1] polyisothiocyanates
Make to be provided with stirrer, be nitrogen atmosphere in 4 mouthfuls of flasks that thermometer, reflux condensing tube, nitrogen are blown into pipe, drop into hexa-methylene diisothio-cyanate 600g, under agitation reactor temperature is remained 130 DEG C, add cyclic trimer catalyzer tetramethyl-ammonium caprylate 1.0g.When the transformation efficiency of isothiocyanate group reaches 30%, add phosphoric acid, stopped reaction.After filtering reacting liquid, film distillator is utilized to be removed by unreacted hexa-methylene diisothio-cyanate.The number-average molecular weight of the polyisothiocyanates obtained is 620, and isothiocyanate group mean number is 3.2.
[embodiment 10]
Drop into acrylic polyol (Setalux1903; NUPLEX society manufactures, trade(brand)name; Hydroxyl concentration 4.5% (resin benchmark), resin solid content 75%) and Production Example 1 in the polyisothiocyanates that obtains, the equivalence ratio of isothiocyanate group and hydroxyl is made to be 1.0, adding relative to resin is the dibutyl tin laurate of 0.5 quality %, mixing butylacetate, prepares the resin combination that solids component is 50%.Utilize spreader that this resin combination is applied to aluminium sheet, make resin thickness reach 40 μm.After room temperature places 10 minutes, keep 10 hours in the baking oven of 150 DEG C, obtain cured coating film.The adaptation of obtained cured coating film is evaluated.Evaluation result lists in table 2.
[embodiment 11]
Drop into 4, the polyisothiocyanates obtained in 4 '-dicyclohexyl methyl hydride diamines and Production Example 1, makes isothiocyanate group be 1.0 with amino equivalence ratio, mixing butylacetate, prepare the resin combination that solids component is 50%, carry out the method identical with embodiment 1 in addition.The evaluation result of cured coating film lists in table 2.
[embodiment 12]
Drop into the polyisothiocyanates obtained in adipic dihydrazide and Production Example 1, the equivalence ratio of isothiocyanate group and hydrazide group is made to be 1.0, mixed ethanol, prepares the resin combination that solids component is 10%, except this carries out the method identical with embodiment 10 in addition.The evaluation result of cured coating film lists in table 2.
[embodiment 13]
Hydrazine monohydrate 36g is dissolved in Virahol 1L, is cooled to 0 DEG C, stir and add methacrylic acid 2-isocyanic ester root conjunction ethyl ester 280g.By filtering, generated solid being reclaimed, utilizing 1h-NMR analyzes, and result is methacrylic acid (2-(Hydrazinecarboxamidederivatives) ethyl ester).
Next, this methacrylic acid (2-(Hydrazinecarboxamidederivatives) ethyl ester) 100g is dissolved in toluene 1L, adds methyl methacrylate 80g and Diisopropyl azodicarboxylate 0.5g, be heated to 80 DEG C.Gather reaction solution after 3 hours, utilize 1h-NMR analyzes, and the double bond that result forms methyl methacrylate disappears.Utilize rotatory evaporator to be removed by toluene distillation, obtain the polymkeric substance with amino urea groups.
Drop into the polyisothiocyanates obtained in this polymkeric substance and Production Example 1, make the equivalence ratio of isothiocyanate group and amino urea groups be 1.0, mixing butylacetate, prepares the resin combination that solids component is 25%.Use this resin combination, carry out the method identical with embodiment 10, carried out the evaluation of cured coating film, the results are shown in table 2.
[embodiment 14]
Hydrazine monohydrate 36g is dissolved in Virahol 1L, is cooled to 0 DEG C, stir and add hexa-methylene diisothio-cyanate 50g.By filtering, generated solid being reclaimed, utilizing 1h-NMR analyzes, and result is 4, the two thiosemicarbazide of 4 '-hexa-methylene.
Drop into this 4, the polyisothiocyanates obtained in the two thiosemicarbazide of 4 '-hexa-methylene and Production Example 1, makes the equivalence ratio of isothiocyanate group and sulfo-amino urea groups be 1.0, mixes butylacetate, prepare the resin combination that solids component is 25%.Use this resin combination, carry out the method identical with embodiment 10, be cured the evaluation of film, the results are shown in table 2.
[reference example 8 ~ 12]
Replace polyisothiocyanates and use isocyanuric acid ester type polyisocyanates (DURANATETPA-100; Asahi Chemical Corp's manufacture, trade(brand)name), carry out the method identical with embodiment 10 ~ 14 respectively in addition, be cured the evaluation of film.The results are shown in table 2.
[embodiment 15]
Drop into the polyisothiocyanates obtained in methacrylic acid-2-hydroxy methacrylate and Production Example 1, the equivalence ratio making isothiocyanate group and hydroxyl is hydroxyl/isothiocyanate group=1.3, adds butylacetate, makes the resin combination that solids component is 50%.By this resin combination with 130 DEG C of heating, continue to be heated to 1till in H-NMR, isothiocyanate group disappears.Next, utilize spreader that this resin combination is applied to aluminium sheet, make resin thickness reach 40 μm.After room temperature places 10 minutes, keep 10 hours in the baking oven of 150 DEG C, obtain cured coating film.The adaptation of obtained cured coating film is evaluated.Evaluation result lists in table 2.
[reference example 13]
Replace the polyisothiocyanates that obtains in Production Example 1 and use isocyanuric acid ester type polyisocyanates (DURANATETPA-100; Asahi Chemical Corp's manufacture, trade(brand)name), carry out the method identical with embodiment 15 in addition.Cured coating film evaluation result lists in table 2.
[embodiment 16]
Carry out the method identical with embodiment 13, manufacture methacrylic acid (2-(Hydrazinecarboxamidederivatives) ethyl ester), next obtain the polymkeric substance of methacrylic acid (2-(Hydrazinecarboxamidederivatives) ethyl ester).
Drop into this polymkeric substance and allyl group isosulfocyanate, make the equivalence ratio of isothiocyanate group and amino urea groups be 1.0, mixing butylacetate, prepares the resin combination that solids component is 25%.Utilize spreader that this resin combination is applied to aluminium sheet, make resin thickness reach 40 μm.After room temperature places 10 minutes, keep 10 hours in the baking oven of 150 DEG C, obtain cured coating film.The adaptation of obtained cured coating film is evaluated.Evaluation result lists in table 2.
[reference example 14]
Replace allyl group isosulfocyanate and use methacrylic acid 2-isocyanic ester root to close ethyl ester, carrying out the method identical with embodiment 16 in addition.The evaluation result of cured coating film lists 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 345g and adipic dihydrazide 384g is added in the eggplant type flask adding the 2L having water 200g and tetrahydrofuran (THF) 800g, after stirring 12 hours at 60 DEG C, add ethyl isothiocyanate 7g further, filtered and recycled is carried out to separated out solid.Next, add above-mentioned solid adding in the 2L eggplant type flask having 2 % by weight aqueous sodium hydroxide solution 1000g, carry out stirring for 8 hours at 100 DEG C, with filter paper, separated out solid is reclaimed.The solid that mensuration reclaims 1h-NMR, identifies structure.The solid obtained in embodiment 17 shown in Fig. 1 1h-NMR spectrum.Infer the resin obtained represented by following formula (124).Number-average molecular weight is 5900, based on Mn/n defined above 1be 150.It should be noted that, X 1by 1h-NMR measures the feed concentrations of sample and the peak (7.26ppm) of chloroform is obtained with the ratio of the integrated value of following the peak (2.6ppm) of the methene chain of the nitrogen-atoms Direct Bonding forming ring.
[embodiment 18]
Make to be provided with agitator, be nitrogen atmosphere in 4 mouthfuls of flasks that thermometer, reflux condensing tube, nitrogen are blown into pipe, drop into hexa-methylene diisothio-cyanate 100g, under agitation reactor temperature is remained 100 DEG C.Thereafter, add tetramethyl ammonium acetate (the 2-butanols 5.0 quality % solution) 2g as catalyzer and stir.Suitably carry out the sampling of reaction solution, 1during H-NMR analyzes, the transformation efficiency of isothiocyanate group reaches the moment of 21%, adds phosphoric acid (the 85 quality % aqueous solution) 0.28g, stopped reaction.Thereafter, further 100 DEG C of heating 1 hour, be cooled to room temperature, filtering reacting liquid utilizes film distillator to be removed by monomer diisothio-cyanate after being removed by insolubles.Monomer diisothiocyanic acid ester concentration is 0.4 quality %, and number-average molecular weight is 860.
By obtained polyisothiocyanates 1h-NMR spectrogram is shown in Fig. 2.Confirmed by NMR spectrogram, the structural unit represented by polyisothiocyanates at least contained (28).Number-average molecular weight is 1200, based on Mn/n defined above 1be 100.It should be noted that, X 1by 1h-NMR measures the feed concentrations of sample and the peak (7.26ppm) of chloroform is obtained with the ratio of the integrated value of following the peak (3.8ppm) of the methene chain of the nitrogen-atoms Direct Bonding forming different trithiocyanuric acid ester ring.
By obtained polyisothiocyanates and acrylic polyol (Dainippon Ink Chemicals's manufacture, trade(brand)name: ACRYDICA-801) mixture, isothiocyanate group/hydroxyl ratio (equivalent) is made to be 1.0, adding relative to coating solid composition is respectively the dibutyl tin laurate of 0.5%, adds the mixed solution of the ethyl acetate/toluene/butylacetate/dimethylbenzene/propylene glycol methyl ether acetate (weight ratio=30/30/20/15/5) as solvent or diluent wherein.With air gun, obtained coating solution is applied on the Copper Foil of thickness 35 μm, being adjusted to dry film thickness is 50 μm, overlapped thickness is the Copper Foil of 35 μm up, sinters after 30 minutes remaining in the baking oven of 120 DEG C, evaluates copper-stripping intensity.The results are shown in table 3.
[embodiment 19 ~ 23]
With the formula shown in table 3 and condition, the method identical with embodiment 18 is utilized to manufacture polyisothiocyanates.Use the polyisothiocyanates obtained, prepare coating solution similarly to Example 18 in addition, copper-stripping intensity is evaluated.The results are shown in table 3.
[table 3]
[comparative example 15]
Replace hexa-methylene diisothio-cyanate and use hexamethylene diisocyanate, be used as tetramethyl ammonium acetate (the 2-butanols 5.0 quality % solution) 0.1g of catalyzer, use phosphoric acid (the 85 quality % aqueous solution) 12mg, utilize the method identical with embodiment 18 to manufacture polyisocyanates in addition.Number-average molecular weight is 1100.Use the polyisocyanates obtained, prepare coating solution similarly to Example 18 in addition, copper-stripping intensity is evaluated.The results are shown in table 4.
[comparative example 16 ~ 20]
With the formula shown in table 4 and condition, utilize the method identical with embodiment 18 to manufacture polyisocyanates, copper-stripping intensity is evaluated.The results are shown in table 4.
[table 4]
[embodiment 24]
Add in the removable flask having bisphenol A type epoxy resin (epoxy equivalent (weight) 189) 100 parts agitator is installed, thermometer, reflux condensing tube, nitrogen is blown into pipe, nitrogen is blown in flask, under agitation be warming up to 150 DEG C simultaneously, after arriving 150 DEG C, continue stirring 30 minutes.Temperature of reaction is maintained 150 DEG C, dripped hexa-methylene diisothio-cyanate 18.5 parts and tetrabutylammonium chloride (medicine pure with light with 2 hours in this condition; PracticalGrade) mixture of 0.05 part.After dropping terminates, temperature is held in 150 DEG C, reacts.By 1the result (Fig. 3) that H-NMR analyzes is known, obtains the compound comprising oxazolidine-2-thioketones ring represented by following formula (125) or (126).The number-average molecular weight of the compound obtained is 2,000, does not find that number-average molecular weight is the material of more than 20,000.It should be noted that, about above-mentioned number-average molecular weight, use shodexA-804, A-803, A-802, A802 of the manufacture of Showa electrician society as post, carried out gel osmoticing chromatogram analysis.Using about 10mg sample dissolution in the tetrahydrofuran (THF) of 10mL as mensuration sample, injection rate is 10 μ L.Compared by the elution time of the polystyrene known with the molecular weight utilizing differential refraction rate detector to observe, obtain number-average molecular weight.Based on Mn/n defined above 1be 220.It should be noted that, X 1by 1the feed concentrations that H-NMR measures sample and the peak (2.3ppm) of toluene that adds as internal standard are obtained with the ratio of integrated value at peak (4.8ppm) of the methyne defining ring structure.
Add the compound, solidifying agent (Dyhard RU 100) and the curing catalysts (glyoxal ethyline) that obtain, make obtained resin combination infiltrate woven fiber glass, and carry out drying, obtain the prepreg that resin content is 50 quality % thus.Overlapping 4 pieces of these prepregs, descend coincidence thickness to be the Copper Foil of 35 μm thereon, at temperature 190 DEG C, pressure 20kg/cm 2condition under heating and pressurizing 60 minutes, produce laminated board thus.For this laminated board, copper-stripping intensity is evaluated.The results are shown in table 5.
[embodiment 25 ~ 29]
Use the compound shown in table 5, utilize the method identical with embodiment 24 to make it react, and carried out 1h-NMR analyzes, and result obtains the compound comprising oxazolidine-2-thioketones ring represented by above-mentioned formula (125) or (126).Use the compound obtained, utilize the method identical with embodiment 24 to evaluate copper-stripping intensity.The results are shown in table 5.
[table 5]
[embodiment 30 ~ 35]
Use the compound shown in table 6, utilize the method identical with embodiment 24 to make it react, and carried out 1h-NMR analyzes, and result obtains the compound comprising following formula (127) or the thiazoline thioketones ring represented by (128).Use the compound obtained, utilize the method identical with embodiment 24 to evaluate copper-stripping intensity.The results are shown in table 6.
[table 6]
[embodiment 36 ~ 41]
Use the compound shown in table 7, utilize the method identical with embodiment 24 to make it react, and carried out 1h-NMR analyzes, and result obtains the compound comprising following formula (129) or the thiazoline-2-ketone ring represented by (130).Use the compound obtained, utilize the method identical with embodiment 24 to evaluate copper-stripping intensity.The results are shown in table 7.
[table 7]
[embodiment 42 ~ 59]
Use the compound shown in table 8 ~ 10, utilize the method identical with embodiment 24 to make it react, and carried out 1h-NMR analyzes, and result obtains the compound comprising oxazolidine-2-thioketones ring represented by above-mentioned formula (125) or (126).Use the compound obtained, utilize the method identical with embodiment 24 to evaluate copper-stripping intensity.The results are shown in table 8 ~ 10.
[table 8]
[table 9]
[table 10]
[embodiment 60 ~ 62]
Use the compound shown in table 11, utilize the method identical with embodiment 24 to make it react, and carried out 1h-NMR analyzes, and result obtains the compound comprising above-mentioned formula (129) or the thiazoline-2-ketone ring represented by (130).Use the compound obtained, utilize the method identical with embodiment 24 to evaluate copper-stripping intensity.The results are shown in table 11.
[table 11]
[comparative example 21 ~ 26]
Use the compound shown in table 12, utilize the method identical with embodiment 24 to make it react, and carried out 1h-NMR analyzes, and result obtains the compound comprising oxazolidone ring represented by following formula (131) or (132).Use the compound obtained, utilize the method identical with embodiment 24 to evaluate copper-stripping intensity.The results are shown in table 12.
[table 12]

Claims (32)

1. a resin, it is the resin with nitrogen-carbon-sulfide linkage, and this nitrogen-carbon-sulfide linkage is made up of nitrogen-atoms, carbon atom and sulphur atom, and these atoms are with this order bonding, at least one in the bonding of described carbon atom and described sulphur atom and the bonding of described carbon atom and described nitrogen-atoms is singly bound
When the number-average molecular weight of this resin be Mn, the quantity of the sulphur atom of the described nitrogen-carbon-sulfide linkage of formation that comprises in every this resin of 1 molecule is n 1time, Mn is more than 500, Mn/n 1be less than more than 50 300, n 1by formula: n 1=X 1mn calculates, X 1represent the quantity of the sulphur atom of the described nitrogen-carbon-sulfide linkage of the formation comprised in this resin of every 1g.
2. resin as claimed in claim 1, wherein, 5% thermal weight loss temperature of this resin is more than 300 DEG C.
3. a resin, it is obtained by the reaction with at least a kind of compound be selected from the group that is made up of monoisocyanates, polyisocyanates, monoisothiocyanates and polyisothiocyanates of the compound with following functional group, at least a kind of functional group in the group that described functional group forms for the 1 valency group be selected from represented by following formula (1), (2), (3), (4) or (5)
-OH(1)-NH 2(2)
4. resin as claimed in claim 3, it is described compound by having following functional group and be selected from the resin obtained by the reaction of at least a kind of compound in monoisothiocyanates and polyisothiocyanates, and described functional group is for selecting at least a kind of functional group in the group of 1 valency group composition represented by free style (1), (2), (3), (4) or (5).
5. the resin as described in claim 3 or 4, wherein, described monoisothiocyanates comprises the compound represented by following formula (30),
R 5-NCS(30)
In formula, R 5represent carbonatoms be 1 ~ 25 aliphatic group, with aromatic group replace carbonatoms be 7 ~ 25 aliphatic group or carbonatoms be the aromatic group of 6 ~ 25.
6. the resin according to any one of claim 3 ~ 5, it has the ring texture of the reaction from the described functional group represented by formula (3), (4) or (5) and isocyanate group or isothiocyanate group.
7. resin as claimed in claim 6, wherein, as the group containing described ring texture, there are more than 2 at least a kind of structural unit be selected from the group that the divalent group represented by following formula (6), (7) or (8) forms
In formula, Y 1represent organic group, with Y more than 2 in a part 1identical or different.
8. a resin, it has more than 2 at least a kind of structural unit be selected from the group that the divalent group represented by following formula (6), (7) or (8) forms,
In formula, Y 1represent organic group, with Y more than 2 in a part 1identical or different.
9. as claimed in claim 7 or 8 resin, wherein, when the number-average molecular weight of this resin be Mn, the quantity sum of the formula (6) that comprises in every this resin of 1 molecule, described structural unit represented by (7) or (8) is n 2time, Mn is more than 500, Mn/n 2be less than more than 50 300, n 2by formula: n 2=X 2mn calculates, X 2represent comprise in this resin of every 1g formula (6), described structural unit represented by (7) or (8) quantity sum.
10. a resin, it is by having the nitrogen-compound of carbon-sulfide linkage and the reaction of polyisothiocyanates obtains, and this nitrogen-carbon-sulfide linkage is made up of nitrogen-atoms, carbon atom and sulphur atom, and these atoms are with this order bonding.
11. resins according to any one of claim 3 ~ 7 and 10, wherein, described polyisothiocyanates comprises the compound represented by following formula (32),
In formula, R 6represent organic group, a represents the integer of 2 ~ 1000.
12. resins according to any one of claim 3 ~ 7 and 10, wherein, described polyisothiocyanates comprises the polymkeric substance of the repeating unit had represented by more than 2 following formula (33),
In formula, R 7represent organic group,
R 8represent organic group or singly-bound,
B represents the integer of more than 1,
G represents 1 or 2,
With R more than 2 in a part 7, R 8, b and g be respectively identical or different.
13. resins according to any one of claim 3 ~ 7 and 10, wherein, described polyisothiocyanates comprises following compound, and this compound has:
The structural unit represented by following formula (40) of more than 2; With
Be selected from least a kind of structural unit in the group that 1 valency, divalent or 3 valency groups represented by following formula (41), (42), (43), (44), (45), (46) or (47) form
Nitrogen-atoms in this compound and carbon atom bonding,
SCN-R 3-(40)
In formula, R 3represent organic group, R 4represent aliphatic group or aromatic group, X 3represent Sauerstoffatom or sulphur atom, with R more than 2 in a part 3, R 4and X 3identical or different respectively.
14. resins according to any one of claim 3 ~ 7 and 10, wherein, described polyisothiocyanates comprises the compound represented by following formula (33),
SCN-R 3-NCS(33)
In formula, R 3represent organic group.
15. 1 kinds of resins, the method for the step of the compound polymerization represented by following formula (33) obtains by comprising by it,
SCN-R 3-NCS(33)
In formula, R 3represent organic group.
The manufacture method of 16. resins according to claim 15, it comprises the following steps: in the presence of a catalyst by the described compound polymerization represented by formula (33).
17. 1 kinds of resins, it has:
The structural unit represented by following formula (40) of more than 2; With
Be selected from least a kind of structural unit in the group that 1 valency, divalent or 3 valency groups represented by following formula (41), (42), (43), (44), (45), (46) or (47) form
Nitrogen-atoms in formula (41), (42), (43), (44), (45), (46) or 1 described structural unit represented by (47) not with the nitrogen-atoms Direct Bonding in structural unit described in other represented by formula (41), (42), (43), (44), (45), (46) or (47)
SCN-R 3-(40)
In formula, R 3represent organic group, R 4represent aliphatic group or aromatic group,
X 3represent Sauerstoffatom or sulphur atom,
With R more than 2 in a part 3, R 4and X 3identical or different respectively.
18. resins as described in claim 13,14,15 or 17, wherein, R 3for aliphatic group or aromatic group.
19. resins as claimed in claim 18, wherein, R 3for the group represented by following formula (301), (302), (303), (304), (305) or (306),
In formula, i represents the integer of 1 ~ 12.
20. 1 kinds of resin combinations, it comprises the resin according to any one of claim 1 ~ 15 and 17 ~ 19.
21. 1 kinds of class coating materials, it is formed by resin combination according to claim 20.
22. 1 kinds of aqueous coatings, it contains resin combination according to claim 20.
23. 1 kinds of resins, it has the molecular chain represented by following formula (10),
In formula, P 1represent aliphatic group and/or aromatic group, Q 1represent the structural unit of more than a kind be selected from group that the divalent group represented by following formula (11), (12), (13) or (14) forms, the P of more than 2 1and Q 1identical or different, n represents the integer of more than 2,
In formula, R 1represent aliphatic group or aromatic group,
X 2and Y 2separately represent Sauerstoffatom or sulphur atom,
With R more than 2 in a part 1, X 2and Y 2it is identical or different respectively,
A Q 1in X 2and Y 2in more than 1 be sulphur atom.
24. resins as claimed in claim 23, wherein, R 1the residue after removing forms 2 isocyanate group of this polyisocyanates from polyisocyanates or the residue remove 2 isothiocyanate groups forming this polyisothiocyanates from polyisothiocyanates after.
25. resins as described in claim 23 or 24, it is obtained by the reaction being selected from least a kind of compound in polyisocyanates and polyisothiocyanates and the compound represented by following formula (20),
In formula, R 2represent aliphatic group or aromatic group,
Y 2represent Sauerstoffatom or sulphur atom.
26. resins as claimed in claim 25, wherein, at least a kind of described compound be selected from polyisocyanates and polyisothiocyanates comprises the compound represented by following formula (31),
XCN-R 1-NCX(31)
In formula, R 1represent aliphatic group or aromatic group,
X represents Sauerstoffatom or sulphur atom.
27. resins as described in claim 25 or 26, wherein, R 2for 1 valency group represented by following formula (201), (202), (203) or (204),
28. resins according to any one of claim 23 ~ 27, wherein, R 1to be carbonatoms the be aliphatic group of 1 ~ 25, the carbonatoms that replaces with aromatic group be 7 ~ 25 aliphatic group or carbonatoms be the aromatic group of 6 ~ 25.
29. resins according to any one of claim 23 ~ 27, wherein, R 1be selected from the alkyl in group that the alkyl represented by following formula (301), (302), (303), (304), (305) or (306) forms,
In formula, i represents the integer of 1 ~ 12.
30. resins according to any one of claim 23 ~ 28, wherein, R 1not containing spiro atom.
31. 1 kinds of solidification compounds, it comprises resin according to any one of claim 23 ~ 30 and solidifying agent.
The manufacture method of the resin described in 32. claims 25 or 26, it comprises the following steps: in the presence of a catalyst, makes to be selected from least a kind of described compound in polyisocyanates and polyisothiocyanates and the described compound represented by formula (20) reacts.
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