TW200806700A - Polyurethane resin and application thereof - Google Patents

Abstract

The invention is to provide a polyurethane resin which is useful as a polyester polyol (a principal ingredient) in an adhesive composition having high sticking properties and adhering properties to a film and having low melting viscosity and also carrying out the solventless coating at low temperatures. The polyurethane resin comprises a polyester polyol consisting of an acid component of which 80% by mole or more is phthalic acid- or isophthalic acid component, and of an alcoholic component of which 50% by mole or more is diethylene glycol component, and having at the molecular end the hydroxy group of on average 0.55 to 5 mole/kg, and a diisocyanate having no cyclic structure in the carbon backbone and a molecular weight of 250 or less.

Description

200806700 IX. OBJECTS OF THE INVENTION: [Technical Field] The present invention relates to a high adhesion and adhesion to a lang, a film of a film or a rubber sheet (hereinafter collectively referred to as "the moon film"), which is quite suitable as The polyurethane resin of the surface, the powder group or the resin component of the composition of the bismuth adhesive is also sufficient for the profit of the _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Method, and Lai_Layer. [Prior Art] Next, trr has a high-density and adhesion coating and ink composition by knife = Γ Generally, it contains a terephthalic acid, an acid component or an isophthalic _ U Wei resin, and the polyglycol ( The following refers to the structure of a polyamine or a polyamine (tetra).红 婢 == _ domain _ red and green towel, if the county ship is a gold-type (type of solvent-free) when it is... t: compared to h _ receiver offerings over i 〇〇 Painter; another ^ " , spring or crepe-like, in the case of plastic bottles followed by _ state two, if the composition of the adhesive is a solvent-containing type, coating, then M d or 疋 dispersed in water The state is to make silly I to volatilize the solvent components. However, 'the composition used for the adhesive composition contains an average of 0. 4~4苴五八 right 疋 的 的 的 的 的 的 、 、 、 、 、 、 、 、 , , , , , , , , 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 i 〇 (the lower temperature below TC, the station degree below i 〇p 9 S is formed. At this time, the composition of the adhesive can enter the surface of the larger plastic enamel (four) red. The batter is not dissolved. The method of the composition of the agent is evaluated as a method in which the environmental load is small because the energy for drying the solvent is not used and the organic solvent is not used.

5〜5__的状的。 The use of the composition of the adhesive agent to form a film thickness of 0. 5~5__ The method is a squeeze roll coating method, and the subsequent composition suitable for the coating method is disclosed in the specification of Patent Document H and Japanese Patent Application No. 20 05-1 8 9329. In the evening, the polyurethane resin which is highly adhesive to the rubber and has a molecular weight secret material Wei resin as a polyol component, and the above-mentioned aromatic banyan tree is known to be polyisocyanate. Polyurethane resin which is denatured into a glutinous rice glutinous rice or an average of G. 〇4~〇. 4 旲g or so of a high molecular weight aromatic polyg resin, not used In the case of an organic solvent, the above-mentioned various resins are difficult to apply because they are used as a composition for a large area of the fourth coating. ^ 'The currently known adhesive composition for the above-described squeeze-roll coating method is t, for example, a wire: 1 or a paste field, for the shirt, and the inorganic acid and organic acid. Or acid anhydrate. 200806700 An acid, etc., has a side effect of having a poor junction. Such as the patented water knife solution, but there is a melting viscosity of the material quality fat, material Xiangsi = ... she 3 money, in order to reduce the material produced after the tree, does not contain the code " field ringing components mixed a lot In the case of the above-mentioned aromatic poly-silanol acid, an organic acid or an acid anhydride, the adhesion and adhesion of the film are insufficient 2 = the adhesive composition, and the following is produced: 2; . 5 — 1 8 9 3 2 2 Revealed, in the above-mentioned brothers: The acid component of her resin, although containing a high concentration of :::=, has a low melt viscosity, and can be used as a film composed of a large amount of poly-lipid. The polystyrene resin exhibits a high-density bond with the film even if it does not contain the acid or acid anhydride of the wrap-around domain. However, if the special wish 2005-1 δ93 is eaten =: as a composition of the adhesive, the composition of the adhesive agent known to him is a problem that requires a long time. If Lang can promote _ fine _ the purpose of the hardening reaction _ chemical agent, the second easy to _ salty resin hardening time. However, in this case, the pQt life of the composition of j is shortened, thus causing a real problem. Beikou, the method of using a solvent-free adhesive composition, and the method of 'edge source', which does not require a solvent, or the method of reducing the environmental load by using no organic solvent, is obtained by the method of "200806700" δ parity, the method of painting a larger area for f q 夕 丨;; 丨θ + & + warfare "post-worm" on the J force ubiquitous is the application of high density, but always unable to obtain突破 旲 。 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 SUMMARY OF THE INVENTION The second case: the purpose of 'providing' is to provide a kind of adhesive (Polyesterpolyo!) (^#]), which is highly adhesive and adhesive to the film. Moreover, the melt viscosity is low, and solvent-free coating can be performed at a low temperature. Moreover, another purpose of this April is to provide, and to lie, and not to reduce the working life with the hardening time test. Agent composition, film laminate method using the same, and film The laminate of the present invention is achieved by the present invention. The invention is based on the provision of 'polyamide-lipid (6), which is a polyurethane resin obtained by reacting a polyol with a test. The characteristics are as follows: ★ When the total polyol is i 〇〇 mol %, at least 8 〇 is the polyester polyol (a) (hereinafter referred to as “polyol (a)”) And when the total acid component of the alfalfa alcohol (a) is 1% mol%, at least 8 〇200,806,700 mol% is a benzene-indole-dioxadicarboxylic acid component;曱 ) ) 成分 成分 成分 成分 成分 当 当 当 当 当 当 当 当 当 当 当 当 当 当 当 当 当 当 当 当 当 当 当 当 当 当 当 当 当 当 当 当 当 当 当 当 当 当 当 当 当 当 当 当The following diol components are bonded to each other; ^ d Molar alcohol (a) has an average of 气 at its molecular end.

When the polyisocyanate is in the form of i 〇 〇 mass %, it is less than 70% by mass of a diisocyanate (b) having no ring structure and having a ring structure of 2 or less in its own structure. In order to achieve the above-mentioned known technology, after reviewing the above-mentioned known technology, the polyamine oxime (c) of the present invention has a lower melting point on the height of the film. Viscosity. That is, the polyurethane tree of the invention of the present invention has a melt viscosity of up to 1 〇 p a in 80 ° C. It is more worth mentioning that the polyurethane resin resin s of the present invention is below. C) 'The melt viscosity of the 8CTC is used to make the polyurethane resin (c), and the sterol (a) is the same composition (ie, the acid component and the polyol component used ^ ^ 疋 疋 奴 ) And compared with the polyester polyol of the same molecular weight as the ♦ urethane resin (c) (a, the degree is lower. The viscous viscosity of the polyurethane resin (c) of the present invention and the above plural, 畆^ ^ a ) In comparison, the first two (four) dimeric filaments (4) C) are considered to be very mellow in the melt viscosity of 200,806,700, but in the present invention, it can be found that the polyurethane resin (C) does not see its smelting viscosity increase, and It is surprising that even the melt viscosity of the upper sterol (a,) is lower. Further, the main agent (1) and the polyisocyanate are used as a main component hardener (I n is formed as a main component, and the above-mentioned polyurethane ((:) is used as a main component of the main (1) (ie, When the amount of the main component is 50 to 100% by mass, the adhesive composition can shorten the time required for curing φ without using a curing catalyst. > The above-mentioned adhesive composition is suitable for use in a large area of the film; j: a film coating of about 5 5 μηα for the production of a film laminate. Press roll coating method. Further, in the above-mentioned adhesive composition of the present invention, 5 (1 〇Fa ^ 7 ammonia side of the main agent (1) is used to make the amount of the curing agent (Η) different to the content of the above-mentioned main agent (1) and the above-mentioned hardening agent ((1) The isocyanate has a Wei group component of at least g 8 mass%, and the person of the rabbit rabbit can only use the composition of the organic compound without the organic solvent. Adhesive layering is often good. Layer processing and laminate nature of the non-sex tree 200806700 fat 0, again, the above polyamine The resin does not reduce the life of the resin with the shortening of the hardening time, and the effect is the main agent of the adhesive agent. By using the adhesive to make it, it can provide a film laminate method with low environmental load and [Lambda] The present invention will be described in more detail below with reference to the preferred embodiment. (IV) Polyurethane S (2) Polyurethane (a) used in the manufacture of the resin (C) When the total amount is 1Q 0 mol%, the acid component is at least 80 mol%, which is the formic acid component and/or the m-benzoic acid component; the silk diterpenic acid component and the j-isophthalic acid component, if If the total acid content is less than 8% of the total acid component, the adhesion of the obtained 7 vinegar resin U) to the film will be lowered. There is a 6-nucleus of the polyurethane (c) = film, with the total acid component. The towel containing the higher affinity of phthalic acid as the rational l)d soil for the above-mentioned neighboring stupid 曱 domain accounted for at least 9 〇 mol% of the total acid component, more preferably 1 QQ mol%. Furthermore, in order to reduce the solubility of the obtained polyurethane resin (C), the solubility of the polyurethane (C) is improved to the solubility of the organic solvent. It alcohol (a) spoon 酉 成 成 成 以 以 邻 邻 邻 邻 邻 邻 邻 邻 邻 邻 邻 邻 邻 邻 邻 邻 邻 邻 邻 邻 邻 邻 邻 邻 邻 邻 邻 邻 邻 = = = = = = = = = = = = = = = = = Stupid one 曱1 is an effective acid component of s, which can be exemplified by phthalic acid and anhydrous o-benzene; and the effective acid component of the (four) stearic acid component is 200806700, which can be exemplified by stupid acid and/or / or its vinegar. In addition, as a 可 成 knife that can produce a total effect, the currently known acid can be used, and the dibasic acid is preferably used in the present invention. Polyalcohol (U) is a polyhydric alcohol formed by the aforementioned acid component and ethanol component, when the total ethanol component is 100% by mole, of which to 対5 Q The mole % must be a diol component formed by combining 2 to 3 filaments having a carbon number of 8 or less. If the above B% component is less than 50% by mole and does not combine with the ship to combine the burning base of Wei 8 or below, the poly-alcohol (a) will increase. Therefore, it is preferred that the content of the above diol component is at least 7 q mol% of the total ethanol component, more preferably 10 mol%. Further, when the diol component is an alkyl group having more than 3 carbon atoms of 8 or less, and the condensed ethanol component is combined by the _ combination, the polyamino hydrazine resin (c) obtained by the polyol (a) is resistant. The New Zealand will be reduced, and the quality deterioration caused by the heat of the polyurethane vine (c) will be more obvious. Therefore, the polyol (a) constituting the polyurethane resin (c:) of the present invention has a heat resistance of the urethane resin (c) which is derived from the above-mentioned diol component, wherein the combination constitutes the aforementioned When the monool component and the alkyl group having 8 or less carbon atoms, the number of ether bonds is preferably 丄. Further, when the diol component is formed of an alkyl group having a carbon number of more than 8 or more, the molecular weight of _ high decreases the content of the phthalic acid (tetra) component as an acid component in the plural (a), and the polyol is passed through the polyol. (a) The obtained polyurethane resin (〇).. II.~ ^ ^ _ ____ * * - - ·--一...._. 12 200806700 The properties of the film are reduced. Therefore, in consideration of the adhesion of the rubber to the rubber, the carbon number of the turbid group constituting the above-mentioned ethanol component is preferably 8 or less. When the total component of the above ethanol component is i QQ mole%, as a diol component constituting at least 50% by mole of ether-bonding 2 to 3 carbon atoms of 8 or less, it is possible to use, for example, Diethylene glycol, triethylene glycol, dipropylene glycol, triethylene glycol, and other diols having a carbon number of 8 or less are additionally opened or two ethylene oxide, propylene oxide, tetra-oxirane, and the like. Other ethanol components which can be copolymerized may be ethylene glycol having two hydroxyl groups, although it is possible to use an ethanol component which is currently known. Further, it is preferred that the polyaminol resin used in the present invention is a polyhydric alcohol having a hydroxyl group having an average Q. 5 5 to 5 mol 8 g at the molecular terminal. When the content of the hydroxyl group is higher than that of the octene (4), the obtained polyurethane (the resin U) will have a lower adhesion. On the other hand, if the content of the hydroxyl group of the polyol U) is less than 5 5 mol/kg, the obtained polyamine-based resin (4)_melt viscosity is increased, and when it is used as an adhesive composition, It is difficult to perform film coating on a large area without a solvent. The method for producing a multi-turn (a) produced by using the polyurethane resin of the present invention may be a method for producing a resin which is currently known, that is, the above-mentioned polydecanoic acid (_baslc acld) and/or Or her purpose, with the top view needs and the catalytic age T, 姊 oxidation to prevent the solution ^ j used in the 140 ~ 25 coffee temperature to produce a polycondensation reaction after the obtained 1 catalyst can be used, but known as titanium oxide More ideal. Oxidation inhibitors 13 200806700 It is preferred to use a phosphite system. The polyisophthalic acid vinegar (8) produced by the polyamino resin (c) of the present invention is a diisocyanate having no ring structure and a molecular weight of 250 or less on a stone counter-moon frame. The preferred diisocyanate is exemplified by cyclobutane diisocyanate S, hexamethylene diisocyanate, 2, 2, 4 or 2 4 , 'dimethyl hexamethylene diisocyanate, lysine Diisocyanate aySmedllsocyanate) and the like. ,

In the manufacture of the square and the wood 'X Ming 1 ammonia from the purpose resin (4), a compound other than the above-mentioned TCg-transactive hydrogen may be used, but the amount thereof is used in all the fields. Full 2 Q Moer%. When the ratio of the other active hydrogen-containing compound is changed, the adhesion of the resin (c) to the film and the adhesion are lowered, and the solubility is also improved. Therefore, it is preferable that the ratio of the other active hydrogen-containing compound is more than i (four) of the component, and more preferably 0 mol%. Other compounds containing hydrazine hydrogen can be used as a resin raw material for polyamines such as polyhydric alcohols and polyamines. In the manufacture of the polyurethane-lipid (e) of the present invention, it is also possible to use polyisocyanate S other than the above, but the other poly-acidic acid does not account for 30 mils of the entire polyiso-acid vinegar. /6. The ratio of the other polyisocyanate g is increased, and the resulting polyurethane resin U is reduced. Therefore, the amount of other polyiso-acidic acid used is preferably 15% by mass or less, and (4)% by weight is more preferable. Other polyisocyanurates can be used as polyisocyanate currently known in poly-resin raw materials, adducts based on cyanic acid, and terminal isocyanide 200806700 prepolymers (prepolymer) )Wait. In the method for producing the polyurethane resin (c) of the present invention, a method for producing a polyurethane resin which is known in the prior art can be applied. That is, the above-mentioned polyol (c), a known other polyhydric alcohols compound or a polyamme compound or the like, an active hydrogen-containing compound, and the above polyisocyanate (b) are regarded as The currently known polyisocyanate compound to be added, if necessary, is coexistent with the urethane catalyst, and then coexisted with an organic solvent as needed at room temperature ~2 $ 〇.匸 is obtained by using polyaddition (polyaddU:·) reaction. The ammonia s-catalyzed catalyst can be used as currently known, but is preferably a stannous salt system. On the top of the polyurethane resin (7) coat k, the right is actually to obtain a binder composition without a solvent, it is desirable to use no organic solvent, but it is also possible to use an organic solvent, and then the currently known method. To remove organic solvents. The organic solvent can be used as currently known, but is preferably _, and/or 1 intended. The main component (polyol) (1)' used in the adhesive composition of the present invention, when the polyol is 1% by mass, wherein 50% to 1% by mass is the upper limit of the polyimide. The following composition of the present invention makes the main agent (! When the total amount of war is 10 (10)% by weight, wherein ◦~50 or less by mass%, although other jujube components are used, the ratio of the above other components to the additive composition is The adhesion of the film and the number of stitches are reduced. The ratio of the portion of the bean is preferably 2.% by mass or less. The mass% is more rational. - The composition of the adhesive of the present invention is used. Hardener (polyisophthalic acid Η 200806700) The content of sucrose is at least 1 (10). If the content of isocyanate is less than 1% by mass, the amount of hardener required to achieve hardening It will increase, and the adhesion of the knot material (G) will decrease, and the adhesion and adhesion of the film of the precipitant composition will decrease. The hardening agent (Ι ι ) will be used for the polyacetal vinegar. The currently known polyisomeric acid s 曰 compound having an isocyanoid content of at least 1 Qf 4%. The main agent (I) and hardener (ί) of the adhesive domain of the present invention, = Wei (hydroxyl, The ratio of the amount of the material of the isocyanate is (i. var. / milyl) to i. 〇~5. 0, preferably i. 5~3. 〇. If the end-to-center system is less than i. 〇, the hardening of the composition of the adhesive cannot be complete. On the other hand, the stoichiometric ratio of the above-mentioned terminal group exceeds 5. 〇, in order to achieve hardening, a large amount of moisture must be provided. It takes a long time to harden. Furthermore, since the content of the poly 2 resin U) is lowered, the adhesion and adhesion of the adhesive composition will decrease with respect to the film. #本(四) If necessary, it can be used with colorants, facets, surfactants, _, _ _, viscosity adjustment 7, levelling agent, stabilizer, UV absorber, etc. Light combination: Bu ^ Lian preventive agent, catalyst, life extension agent, plasticizer, filling _ to obtain. Especially with regard to the catalyst, although the carving has been added for the hardening time = use, but the reduction will also produce life. Disadvantages of the invention. In the case of the hybridization method, the use of # is also less than the conventional method of the prior art, which is more effective than the conventional method. The adhesive composition of the present invention, wherein Not wave The composition is at least 98% by mass, and it is ideal for those who do not actually contain organic solvents. The reason why the "actually" nonvolatile matter is less than 100% by mass is considered to be the addition of a trace amount of mixed moisture, or polyiso# (1) The case where the acid is produced by reacting with water and the acid gas generated by the decomposition of the acid gas or the light-mixing agent will form a volatile component.

A method of laminating a film using the adhesive composition of the present invention can be applied to a conventionally known lamination method. Basically, the main agent (1) is mixed with the hardener ((1) by heating and melting, and then formed into a subsequent composition, and after the application of the adhesive composition 2, it is combined with other coffee, tablets, miscellaneous and other Wei substrates. Then, the method of hard pouring under normal temperature or heating conditions, but the composition of the adhesive can also be red 姊 _ two sides, if necessary, in order to promote the composition of the adhesive after the coating, can also be dispersed Adding a heating surface or a placing step. It is desirable to appropriately mix and mix the ingredients to be used in the clothing set to be used as an adhesive composition. The adhesive agent is prepared by mixing the main agent (1) with a hardener (丨丨). In the case of mixing, the hardening reaction is carried out to make the viscosity increase slowly. Therefore, it is not preferable to prepare a large amount of spare materials. The coating method of the present invention can be turned up to the prior art. Specifically, "can be used for the tube coating method, the reverse drum coating method, the first one---__ the preparation method of the adhesive composition of the present invention, the main agent (!) and the hardening Agent (II) uses different pumps, The mixer is used to automatically calculate the supply and 200806700 'wood curtain type; k-Buffaloburg cloth method. The coating thickness and coating method of the adhesive composition are based on the characteristics of the film substrate (coated film) or necessary For example, when the substrate (4) and the smoothness of the adhesive surface are high and the use of a high adhesive strength is not required, the coating film thickness of the adhesive composition is preferably about 丄5 to 5 mm, and the coating in this case is preferable. The method is ideal for the extrusion roller coating method. Moreover, the thickness of the coating film is thicker, the surface of the film is poor, and the thickness of the coating composition of the carrier composition is about 5 ~Working _ is ideal and is ideal for methods other than holding roller coating method. &quot; The film base material of the lacquer is laminated to the surface of the film. Polyolefins, polystyrene, polychloroethylene, polystyrene and its ethylene copolymers represented by ethylene and polypropylene, poly- _ _ _ _ _ _ PET) is a variety of naphthalene film foams such as polyester vinegar, and The silk is coated with (four) vinylidene chloride as a representative of various polymer coating agents currently known, formed by metal evaporation, oxidation of oxidized stones, oxidation of the inorganic layer represented by oxidation, etc. In addition, metal materials such as thorns, saki, etc.: woven fabrics, cloths, papers, etc., and other substrates that have been laminated in advance. : The performance of the _ _ _ _ _ _ _ _ There is no substrate, and a laminate using these film substrates has a laminate of the features of the present invention. Fields (Examples) 200806700 Hereinafter, synthesis examples, examples, comparative examples, and reference examples are given, and the present invention is specifically described. [Synthesis Example a-1 to a-1]] &lt;Polyol (a 1 : Method for Producing Synthesis Example a-1)&gt; The flask was charged with anhydrous o-dicarboxylic acid 5 3 8 g, digan. The alcohol 4 6 2 avoids the triphenyl SI ig of the dish, and the mixture is heated under a nitrogen stream while stirring (10 hours to f 3 〇 ° C), and then the vinegarization reaction is carried out while steaming the water. In the water-steamed crane just stopped the miscellaneous, adding tetra^n-oxytitanium polymerization grade jealousy, ask the temperature to 250 °C 'polymerization under the reduced pressure of 1 Q t 〇rr to obtain hydrogen and oxygen Polyol (al) having a base concentration of 1.9 mol/kg. The polyol u丄) has a melt viscosity of 8 TC·9 pa·s at TC. The production method of polyhydric alcohol (a 2 : Synthesis Example a-2) is the same as that of the polyol (a 1). From anhydrous phthalic acid 5 5 4 and diethylene glycol 4 6 2 g, a polyol having a hydroxyl group concentration of 1 mol/kg 2) was obtained. The polyol (a 2) has a melt viscosity at 8 (TC of 〇·5 Pa·s. &lt;Production method of polyalcohol (a 3 : Synthesis Example a-3)> is the same as multi-turn (a 1 ), From the stupid divalent 6 Q 3 g and diethylene glycol ^ to j morning 1.8 km / kg of polyol (a 3). 19 200806700 ° Xuan Xi Xin (a 3) at 80 ° C The melting degree is 1 2 P a · S < 兀 兀 (a 4 : synthesis example a - 4) manufacturing method > 广 夕 § § (a 1 ) is the same, from anhydrous o-dicarboxylic acid 4 2 9 g And digan ▲ # to a hydroxyl group concentration of 5 · 3 mol / kg of polyol (a meta (a 4 ) at 80 ° C melt viscosity is q. 2 pa · s ( < 兀 兀 % ( a 5: The production method of Synthesis Example a-5) was the same as the polyol U 1), from the anhydrous phthalic acid 5 6 8 children, to the chlorooxy group concentration "and the oxime alcohol (a 5) at 8 Torr. (Production method of melt viscosity under the condition of &gt; 3 &gt; Ό &lt; Polyol U 6 : Synthesis Example a

Same as the polyterpene alcohol U1), from the pair of dimethyl g_3g and the two turns of 6 2 g, 'the hydroxyl group concentration of 2. i molar eight g of polyol (w the polyol U6) at 8CTC The melt viscosity is 6 〇 Pa · s. Further, the resin is in a state of 8 lions - a part of the crystal component exhibits dispersed sand &lt; a polyol (a 7 and a polyol (a synthesis example a-7) manufacturing method &gt; g and neopentyl -: ~'-- — a 1) Same as 'from anhydrous phthalic acid ^^ ------._ 20 200806700 ;). In the crucible, a polyhydric alcohol having a hydroxyl group concentration of 2.1 mol/匕g (a) a core 颂 U7) has a melt viscosity W30 Pa.s. <Eight 1 (a8: Synthesis Example a-8) Manufacturing Method> 4 Shouxi Fanzi (a 1 ) is the same, from adipic acid 5 5 9 g and 1,4-butanediol ^ 4 丄 / towel, A polyol (a 8 ) having a hydroxyl group concentration of 2 mol/kg was obtained. The melting viscosity at 8 G ° C is Q2Pa . s. <The production method of ceramyl alcohol (a 9 : Synthesis Example a-9)&gt; is the same as the oxime alcohol (a 1), from adipic acid 5 8 3 g and 1,4-butanediol 4 1 7 g A polyol (a 9 ) having a hydroxyl group concentration of 1 mol/k was obtained. The melting viscosity of the oxime (a 9 ) at 8 〇 ° C is 〇 · 5 P a · s.

The above polyols a 1 to a 9 are shown in Table 1. Table 1 ---—^__^ Synthetic Example a — 1~a — 9 Polyol (a) —~~~~~~ al a2 a3 a4 a5 a6 a7 a8 a9 Acid Component~-------- -----S APA APA I PA APA APA TPA APA AA AA Ethanol component DEG DEG DEG DEG DEG DEG NPG BD BD Hydroxyloxy group concentration ~ mol / kg 1.9 1 1.8 5.3 0.5 2.1 2.1 2 1 21 200806700 (abbreviation) APA : anhydrous phthalic acid IPA: isophthalic acid TPA: terephthalic acid AA: adipic acid DEG: diethylene glycol NPG: neopentyl glycol BD · · 1, 4-butanediol example c 1 to c 4 , Comparative Example c 1 to c 6 &lt;Polyurethane Resin ((:)&gt; Example c1 (Polyurethane Resin c1) A flask was charged with a polyol (a 1 ) 1 0 5 3 g and hexamethylene diisocyanate. 7 3. 4 g, under the nitrogen flow, while stirring for 8 hours in 7 51: to obtain a polyurethane resin with a hydroxyl group concentration of 1 mol / kg • ( c 1 ) The resin has a melt viscosity of 4 P a · s at 80 ° C. Example c 2 (polyurethane resin c 2) is the same as polyurethane resin (c 1 ), from polyol (a 1 ) 10 5 3 g and In the lysine diisocyanate 9 0. 8 g, the hydroxyl group concentration is 1 mol/ Kg of polyurethane resin (c 2 ). The melt viscosity of the resin at 80 ° C is 5. 7 P a · s ° 22 200806700 Comparative Example c 1 (Polyurethane resin c 3) ( c 1 ) , ( a 1 ) 1 〇5 3 g and isophorone diisocyanate, plant u, ^ t ^ 9 4, 6 g Comparative Example c 2 (polyammonium c 4) and 4 human urethane resin (C 1 )冋 冋 &quot;, 夕 - a) the same, 攸 凡 凡 凡 (a 1 ) 1 〇 5 3 g, - this methane diisocyanate (diphenylmethane 1S 〇 Cyanate) 1 〇 5 · 2 g, get 氡 oxygen, Produce] 笪 ( (e4). The paste viscosity in the paste is 18 Pa. s 实施 Example c3 (polyurethane resin c5) and hexane resin (C 1 ) are the same, from the polyol U 2 ) 1 〇 5 3 a · s

In the subsequent 4 2.4 g, the hydroxyl group is obtained. 5 0 mol/min 曰 fat (C 5 ) 熔融 The melt viscosity of the resin in 80 〇 C is 9 F c A case c 4 (polyammonium) The vinegar resin 200806700 is the same, from the polyol (a 3) 10 5 3 gg, the polyoxyc with a hydroxyl group concentration of 1 mol/kg and the polyaluminium sulphate (and hexamethylene diisocyanide) Uw two...T-secret 丄, k 咖). The melt viscosity of the grease in 80 C is 9. 5 pa . S ° Comparative example u urethane resin c 7) and polyurethane resin um, From the polyol (a4 and bismuth diisocyanate / ^ 3 g polyurethane _ / to obtain a hydroxyl concentration of 1 mol 8 g of &quot;9 C7). The melt viscosity of the resin at 80 ° C is 6. 5 Pa . S 〇 Comparative Example c4 is intended to be e8)

And ::: resin (cl) is the same, from the polyol "6) U and hex - listening 1 8 8 9. 2 g, the concentration of hydroxyl group is obtained] Mohr / full fat (: 8). Face fusion 5! pa = Na (four) Xia 1 plum is now divided into the same as the polyurethane tree (c 1 ), only because of the 7 R ",, once% is 1 2 Ot, from the polyol (7 plant Fajin 仃 ^ : 7) 105 3g2 24 200806700 In a hexose-isolated acid brewing 89· 2 g, a hydroxyl group concentration of a molybdenum (tetra) polyurethane resin (c 9 ) is obtained. The melt viscosity of the resin at 80 ° C cannot be measured (more than $ Comparative Example c 6 (polyurethane resin c 1〇) and polyurethane resin (c 1) are the same, from polyol (a 8) 丄〇 5 and Isocyanic acid _ 8 1. 6 g in 'to get the hydroxyl concentration 丄 耳 八 贼 贼 ( ( ( ( ( ( 。 。 。 。 。 。 。 。 。 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该The melt viscosity of the polycarbonate (aa 5, a 9 ) with a similar resin and hydroxyl group concentration at 8 〇〇c is shown in Table 2-2 for reference hydroxyl concentration Mo/kg, —__ 8 ° ° C melt viscosity Pa · s

Polyurethane Resin (C) ___ Polyol (a) ~^.______ Polyisocyanate (b), _____ with or without ring structure 25 200806700 (abbreviation) HDI: hexamethylene diisocyanate LDI: lysine diisocyanate g IPDI: different Buddha Mercapone diisocyanate MDI : 4, 4' dibenzoxane diisocyanate Table 2 - 2 Comparative Example (Reference) c4 c5 c6 Polyurethane Resin (C) c8 c9 clO — — — Polyol (a) a6 a ? a8 a2 a5 a9 polyisocyanate (b) HDI HDI HDI — — — with or without ring structure benefits φ \ 益 4\W benefits — — hydroxyl concentration Mohr / kg 1 2 1 1 0.5 1 80 ° C melt viscosity Pa · s 51 2500 1 5 12 0.5 (abbreviation) HDI: hexamethylene diisocyanate &lt;Production method of compounding agent (a 2-9)&gt; Polyol (a 2 ) 750 g and polyol (a 9) ) 2 5 0 g mixed, 26 200806700 The main ingredient (a 2 - g ) is obtained. The concentration of the hydroxyl group in the main component is 丄mol/kg 〇&lt;the method of producing the hardener (II a)&gt; the AKENATE D-l65N5〇〇g of the Takeda Pharmaceutical Industry and the C 0 of the Japanese polyurethane R 0 N a Τ Ε Η X 5 0 〇g is mixed to obtain a hardener (II a). The isocyanate group concentration of the hardener was 5.3 mol/kg • (the isocyanate group content was 22% by mass). &lt;Manufacturing Method of Curing Agent (II b)&gt; The flask was filled with Asahi Kasei DURANATE 6 5 g and polyterpene alcohol (a 1 ) 13 5 g, and the mixture was stirred at 75 C under a nitrogen stream while stirring. 8 hours of polyaddition reaction to obtain a hardener (^ Xia b). The hardener had an isocyanate group concentration of 4·5 mol/kg (isocyanate-based content of 19% by mass). Examples 1 to 5 and Comparative Examples 1 to 12 &lt;Adhesive Compositions> As a main component, the polyol (a 2, a 5 , a 9 ) obtained in the above Synthesis Example can be blended with a polyol (a 2 - 9) The polyurethane resin (c 1 to c) and the curing agent (II a, II b ) were mixed at a ratio shown in Table 3 to obtain an adhesive composition of the present invention and a comparative example. - -·· 二产-···. __ - -- ^ - - Γ* - ♦—— ... :·-·- ...- . ----- · 27 200806700 [Evaluation Results] Table 3 - 1

Substance Composition Example 1 Comparative Example 1 Comparative Example 2 Example 2 Example 3 Comparative Example 3 Main agent (I) cl cl cl cl c2 c3 Hardener (II) Ila Ila Ila lib Ila Ila The amount of the main agent (g) 100 100 100 100 100 100 Hardener dosage (g) 40 17 104 47 40 40 NC0/0H ratio 2·1 0· 9 5.5 2. 1 2. 1 2.1 Coating properties 〇〇〇〇〇 Δ Aluminium adhesion 〇 XX 〇〇〇 evaluation PET 〇 〇 〇 〇〇〇 hardening 〇 〇 〇〇〇

28 200806700 Table 3-2 Adhesive Composition Comparative Example 4 Comparative Example 5 Example 4 Comparative Example 6 Example 5 Comparative Example 7 Main Agent (I) c4 a2 c5 a2-9 c6 C7 Hardener (II) Ila Ila Ila Ila Ila Ila main agent compounding amount (g) 100 100 100 100 100 100 Hardener compounding amount (g) 40 40 20 40 40 40 NC0/0H ratio 2. 1 2.1 2.1 2. 1 2. 1 2. 1 Coating property Δ 〇 〇〇〇〇Aluminum adhesion 〇〇〇X 〇X Evaluation PET Next 〇〇〇X 〇X Harden 〇X 〇X 〇〇

29 200806700 Table 3 — 3

Subsequently composition Comparative Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 11 Comparative Example 12 Main agent (I) a5 c8 c9 clO a9 Hardener (II) Ila Ila Ila Ila Ila Total amount of the main agent (g) 100 100 100 100 100 Hardener compounding amount (g) 20 40 40 40 40 NC0/0H ratio 2. 1 2.1 2_ 1 2.1 2.1 Coating property Δ Δ X 〇〇 Aluminum adhesion 〇〇 ND XX Evaluation PET Subsequent 〇〇 ND XX Hardenability X 〇ND 〇X Regarding the evaluation described in the table, the method is as follows. (Hydroxyl concentration) The evaluation object was measured based on JIs K 0070. (Isocyanate group concentration) The evaluation object was measured based on JIs K 1603. (Fused Viscosity) —- - 30 200806700 . The evaluation object was measured for the melt viscosity at 8 〇t: using a BM-type spin meter (r〇tati〇nai v1SCOmeter). (Applicability) Evaluation was carried out by a squeeze coater at 2 * suitability. The best time for the work is 'applied to it. Good appearance, △: outer 胄n coating is not smooth. · No: (aluminum foil adhesion) For aluminum foil with a thickness of 2 5 _, the film will be applied After the work, the thickness of the 〇 _, _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The vinyl resin was found from the upper round of the aluminum foil. The direct locking 〇: the substrate was broken, and x:=: the peeling state was evaluated. Information, plum 'nd: can not be coated without (PET adhesion) relative to the thickness of 25_! ^丁, after the film coating, and the factory to reinforce the coating film with 2_ of the straight-chain low-density polyethylene resin, 'in the Θ 纟 to the corona surface ^ ^ ^ under &amp; After 7 days, in 2008-0600 5 C, the coating film was directly locked and its peeled state was evaluated. When the low-density polyethylene resin is peeled off from PET, it is impossible to apply ND to the ND. The substrate is broken. No data is available. X: It is easy to peel off (hardenable). When PET adhesion is evaluated/continued He was not evaluated for the hardened state of the docking agent composition just after 3 days. 〇. Hardening (no adhesion), χ: not

^ Culture Q has sticky), ND: I 忐 Adhesive coating without data... As described above, 'With the invention—the film has high adhesion/, money_fat' _ is a surprisingly low viscosity and thin When the composition of the polyisocyanate is excellent, the composition of the polyisocyanate is hard, and it is used as a special product. These resins are applicable not only to resins. ^Can be used as a high adhesion adhesive for the film [Simplified description] [Main component symbol description]

Claims (1)

200806700 X. Patent Application Range: Production of alkaloids and polyisocyanates 1. A polyurethane resin (c) characterized by the above-mentioned multi-Tt alcohol (in the overall diversity) When the alcohol is i 〇〇 mol %), at least 8 〇 Mo _ _ ol (a), and the poly lactic acid (a) has an overall acid composition of 100% by mole, at least 8 qmol% is stupid-◦-dicarboxylic acid component and/or benzene-m-dicarboxylic acid component, The diol component produced afterwards, the above polyester polyalcohol (a) has a hydrogen radical at the molecular end of the molecule being 〇/kg, and ... if the total ethanol component of the above polylactic acid polyol (a) is ^ 〇〇 Mo When the ear is at least, at least 50% of the mole is a filament having a carbon number of 8 or less, and by combining 2 to 3 5 to 5 moles of the above polyisocyanic acid, when the total polyisocyanate is i 0 〇 mass _, Among them, H 0% by mass is a polyisocyanate of a diisocyanate (b) having a ring structure and a molecular weight of 25 Å or less in the structure. 2. The polyurethane resin (c) according to the invention of claim 2, which has a melt viscosity of 10 P a · s in 8 generations. 3. The polyurethane resin (c) has a melt viscosity in 8 (TC) and is used in the manufacture of a polyurethane tea (c), as described in the patent application. The poly(s) is the same as the composition of the same, and the solubility viscosity of the polyurethane-lipid (7) is lower than that of the polyhydric alcohol. 33 200806700 4· The composition of the sword, Ritter is — r T , t broken silk from the main ingredient of the beer as the main component HU I ), formed by the hardening of the polyisocyanate as the main component, In the composition of the agent, if the total amount of the main agent (1) is 1 (10)% by mass, the amount of 5 〇 〇 〇 quot 量 量 必须 必须 必须 必须 必须 必须 必须 专利 专利 专利 专利 专利 专利 专利The content of isocyanate in ammonia vinegar = U ί π must be at least 10% by mass, The stoichiometric ratio of the terminal group of the above-mentioned main agent (1) and the above-mentioned hardener π 1) (exclusive basis / hydrogen group) red Q~5. 0, non-volatile content of at least 9 δ mass /, and on the shellfish It is a composition that does not contain an organic solvent. 5. A method of laminating, characterized in that a method of laminating a plurality of sheets of film or paper is carried out by using an adhesive composition as described in item 4 of the article. 6. A laminate body characterized in that it is formed by laminating a plurality of sheets of film or paper using an adhesive composition of the fourth application of the patent application. 34