CN1277894C - Solventless adhesive and its application - Google Patents

Abstract

A nonsolvent type adhesive composition comprises a polyester polyol (A) having a high glass transition temperature and a large number average molecular weight, a polyester polyol (B) having a low glass transition temperature and a small number average molecular weight, a three-functional isocyanate compound (C) formed with an alicyclic diisocyanate compound or an aromatic diisocyanate compound (D), a trifunctional isocyanate compound (E) formed from an aliphatic diisocyanate compound (F) and a polybasic acid anhydride (G).

Description

Non-solvent adhesive and utilization thereof

Technical field

It is a kind of suitable to food product pack, medical treatment product packing, toiletry bag package material etc. to the present invention relates to, have excellent adhesiveness the non-solvent adhesive composition, use this non-solvent adhesive composition and have binder layer sheet material and manufacture method thereof, use this non-solvent adhesive composition and have the sheet layered product and the manufacture method thereof of sheet material and other flat substrates of binder layer.

Background technology

With between the various plastics films, various plastics film and tinsel, various plastics film and evaporated film (films of various metals of evaporation or metal oxide etc.) etc. fit and the layered product that forms its many wrapping material as various fields, purposes.For example, only in the food product pack field, just have layered product self is made pouch, in this sack, fill various food and with the peristome sealing, also have and in having the teacup shape plastic containers of recess, fill various food, stick layered product at peristome.In addition, the content of filling is also varied, has tealeaves, thin pancake, cooky, French fries etc. to be in the decorating film of drying regime, and fraction is also arranged.Fraction also is various, and it comprises congee for example, curry that culinary art is good, tomato-sauce, so-called sports beverages, various food flavourings etc.

Solid state food needs to carry out heat treated hardly after being filled in the wrapping material.On the other hand, be purpose with the sterilization, liquid food will carry out heat treated sometimes after filling, or will immerse in the hot water together with wrapping material sometimes when eating this food, or carries out the boiling heating.

As the adhesive for lamination that the plastics film that makes various plastics films and evaporation metal or tinsel are fitted, its utilization be reaction between hydroxyl and the isocyanate group.Promptly, what use is to cooperate polyisocyanate compounds and the two solution curing type organic solvent type tackiness agents that form in organic solvent solution always, wherein, organic solvent solution forms in organic solvent by the resin dissolves that vibrin or polyether(poly)urethane resin etc. is contained hydroxyl.

In recent years, because the requirement of the reinforcement of the improvement of labor operation environment, fire service law, volatile organic compounds (VOC) discharge regulation etc. in atmosphere, tackiness agent to take off the organic solvent tendency obvious day by day, to the transformation of solvent free carry out (with reference to the spy open flat 07-097557 communique, the spy opens 2000-154363 communique etc.).

Non-solvent adhesive is because its solvent-free cause in order to ensure its coating, need make the viscosity of tackiness agent reduce.Therefore, reach low viscosity, compare with the situation of organic solvent type tackiness agent in order to make tackiness agent, make with regard to having in the tackiness agent resinous molecular weight diminish.

If make in the tackiness agent resinous molecular weight diminish, then compare its poor adhesion with the tackiness agent of organic solvent type.Particularly to the plastic film of evaporation metal or the poor adhesion of tinsel.

Summary of the invention

It is a kind of suitable to food product pack, medical treatment product packing, toiletry bag package material etc. to the object of the present invention is to provide, and in the time of the coating excellence, also has the non-solvent adhesive composition of excellent adhesiveness.

In addition, another object of the present invention is to provide a kind of not only after distillation, even and pass through for a long time the non-solvent adhesive composition that the bounding force between tinsel and plastic film also reduces fewly.

In addition, the present invention also aims to provide a kind of sheet material and the manufacture method thereof of the binder layer that uses this binder composition, the sheet material that has the binder layer that uses the non-solvent adhesive composition and the sheet layered product and manufacture method thereof of other flat substrates of having.

Above-mentioned and other purpose of the present invention, feature and advantage can be known from following record and see.

The invention provides following means:

＜1〉a kind of non-solvent adhesive composition is characterized in that it contains

The second-order transition temperature of (1) 5～70 weight % be 10～40 ℃, number-average molecular weight be 500～2000 polyester polyol (A), 20～95 weight % second-order transition temperature for-70～0 ℃, number-average molecular weight be 500～2000 polyester polyol (B) and 0～30 weight % monofunctional alcohol (C) (polyester polyol (A) and (B) and monofunctional alcohol (C) add up to 100 weight %);

(2) the trifunctional isocyanates compound (D) that (i) forms by alicyclic diisocyanate compound or aromatic diisocyanate compounds and (wherein by the trifunctional isocyanates compound (E) of aliphatic diisocyanate compound formation, isocyanate group and above-mentioned polyester polyol (A) that above-mentioned trifunctional isocyanates compound (D) adds up in reaching (E), (B) and the number of the hydroxyl that adds up in the monofunctional alcohol (C) than being isocyanate group/hydroxyl=0.7/1.0～1.5/1.0), or the trifunctional isocyanates compound (D) that (ii) forms by alicyclic diisocyanate compound or aromatic diisocyanate compounds, trifunctional isocyanates compound (E) by the aliphatic diisocyanate compound formation, and diisocyanate cpd (F) (wherein, above-mentioned trifunctional isocyanates compound (D), (E) and the isocyanate group and the above-mentioned polyester polyol (A) that add up in the diisocyanate cpd (F), (B) and the number of the hydroxyl that adds up in the monofunctional alcohol (C) than being isocyanate group/hydroxyl=0.7/1.0～1.5/1.0); And

(3) multi-anhydride (G).

＜2〉according to above-mentioned＜1〉a non-solvent adhesive composition of putting down in writing, it is characterized in that it contains the oxygen acid or derivatives thereof (H) of phosphorus.

＜3〉according to above-mentioned＜1〉or＜2〉a non-solvent adhesive composition of putting down in writing, it is characterized in that polyester polyol (B) is the polyester polyol (B2) that does not contain the polyester polyol (B1) of ehter bond and/or contain ehter bond.

＜4〉a kind of non-solvent adhesive composition is characterized in that it is combined with:

(1) second-order transition temperature that contains 5～70 weight % be 10～40 ℃, number-average molecular weight be 500～2000 polyester polyol (A), 20～95 weight % second-order transition temperature for-70～0 ℃, number-average molecular weight be 500～2000 polyester polyol (B) and 0～30 weight % monofunctional alcohol (C) (polyester polyol (A) and (B) and monofunctional alcohol (C) add up to 100 weight %) and the 1st composition of multi-anhydride (G) and

(2) (i) contain the trifunctional isocyanates compound (D) that is formed by alicyclic diisocyanate compound or aromatic diisocyanate compounds and reach the trifunctional isocyanates compound (E) that is formed by the aliphatic diisocyanate cpd; Or (ii) contain the trifunctional isocyanates compound (D) that formed by alicyclic diisocyanate compound or aromatic diisocyanate compounds, the trifunctional isocyanates compound (E) that is formed by the aliphatic diisocyanate cpd and the 2nd composition of diisocyanate cpd (F)

Make above-mentioned trifunctional isocyanates compound (D) reach (E) middle isocyanate group and the above-mentioned polyester polyol (A) that adds up to, (B) and the number of the hydroxyl that adds up in the monofunctional alcohol (C) than being isocyanate group/hydroxyl=0.7/1.0～1.5/1.0 or above-mentioned trifunctional isocyanates compound (D), (E) and the isocyanate group and the above-mentioned polyester polyol (A) that add up in the diisocyanate cpd (F), (B) and the number of the hydroxyl that adds up in the monofunctional alcohol (C) than being isocyanate group/hydroxyl=0.7/1.0～1.5/1.0.

＜5〉according to above-mentioned＜4〉a non-solvent adhesive composition of putting down in writing, it is characterized in that the 1st composition contains the oxygen acid or derivatives thereof (H) of phosphorus.

＜6〉according to above-mentioned＜4〉or＜5〉a non-solvent adhesive composition of putting down in writing, it is characterized in that polyester polyol (B) is the polyester polyol (B2) that does not contain the polyester polyol (B1) of ehter bond and/or contain ehter bond.

＜7〉according to above-mentioned＜2〉or＜5〉a non-solvent adhesive composition of putting down in writing, it is characterized in that, for the polyester polyol (A), (B) and the monofunctional alcohol (C) that add up to 100 weight parts, the oxygen acid or derivatives thereof (H) of phosphorus is 0.01～5 weight part.

＜8〉according to above-mentioned＜1 〉～＜7 in the non-solvent adhesive composition of any one record, it is characterized in that the trifunctional isocyanates compound (D1) of trifunctional isocyanates compound (D) for alicyclic diisocyanate compound or the esterification of aromatic diisocyanate compounds cyamelide are formed.

＜9〉according to above-mentioned＜1 〉～＜8 in the non-solvent adhesive composition of any one record, it is characterized in that trifunctional isocyanates compound (E) is for the biuretized trifunctional isocyanates compound (E1) that forms of aliphatic diisocyanate compound.

＜10〉according to above-mentioned＜1 〉～＜9 in the non-solvent adhesive composition of any one record, it is characterized in that diisocyanate cpd (F) is alicyclic diisocyanate compound (F1).

＜11〉according to above-mentioned＜1 〉～＜10 in the non-solvent adhesive composition of any one record, it is characterized in that multi-anhydride (G) is the trimellitate acid anhydride shown in following formula (1) or (2).

＜12〉a kind of sheet material that has binder layer is characterized in that, its by under heating with above-mentioned＜1～＜11 in the non-solvent adhesive composition of any one record one side at least that is applied to flat substrates go up and form.

＜13〉a kind of manufacture method that has the sheet material of binder layer is characterized in that, it is included in heating down with above-mentioned＜1 〉～＜11 in the non-solvent adhesive composition of any one record be applied to the flat substrates step on the one side at least.

＜14〉a kind of sheet layered product is characterized in that, it is by to above-mentioned＜12〉binder layer of the sheet material that has binder layer of a record and other flat substrates carry out lamination and form.

＜15〉a kind of sheet laminated body manufacturing method is characterized in that, it is included in heating down to above-mentioned＜12〉binder layer and other flat substrates of the sheet material that has binder layer of a record carry out laminated step.

＜16〉a kind of sheet laminated body manufacturing method, it is characterized in that, it is included in heating down with above-mentioned＜1 〉～＜11 in the non-solvent adhesive composition of any one record be applied to flat substrates at least one side go up and form binder layer, under heating, other flat substrates and this binder layer are carried out laminated each step then.

As other preferred examples of non-solvent adhesive composition of the present invention, it comprises for example following example.As detailed below, can carry out appropriate selection to these examples according to the purposes of employed non-solvent adhesive composition, essential rerum natura etc.

＜17〉a kind of non-solvent adhesive composition, it is characterized in that, its second-order transition temperature that contains 30～70 weight % is 10～40 ℃, number-average molecular weight is 500～2000 polyester polyol (A), the second-order transition temperature of 20～50 weight % is-70～0 ℃, number-average molecular weight is 500～2000 polyester polyol (B), the monofunctional alcohol of 5～30 weight % (C) (polyester polyol (A), (B) and monofunctional alcohol (C) add up to 100 weight %), the trifunctional isocyanates compound (D) that forms by alicyclic diisocyanate compound or aromatic diisocyanate compounds, trifunctional isocyanates compound (E) (wherein, above-mentioned three palaces energy isocyanate compounds (D) and (E) isocyanate group and the above-mentioned polyester polyol (A) of total by the aliphatic diisocyanate compound formation, (B) and the number of the hydroxyl that adds up in the monofunctional alcohol (C) than being isocyanate group/hydroxyl=0.5/1.0～1.5/1.0), and multi-anhydride (G).

＜18〉a kind of non-solvent adhesive composition, it is characterized in that, it is combined with the second-order transition temperature that contains 30～70 weight % is 10～40 ℃, number-average molecular weight is 500～2000 polyester polyol (A), the second-order transition temperature of 20～50 weight % is-70～0 ℃, number-average molecular weight is 500～2000 polyester polyol (B), the monofunctional alcohol of 5～30 weight % (C) (polyester polyol (A), (B) and monofunctional alcohol (C) add up to 100 weight %) and the trifunctional isocyanates compound (D) that forms by alicyclic diisocyanate compound or aromatic diisocyanate compounds of the 1st composition of multi-anhydride (G) and containing and by the 2nd composition of the trifunctional isocyanates compound (E) of aliphatic diisocyanate compound formation, make above-mentioned trifunctional isocyanates compound (D) and (E) in the isocyanate group and the above-mentioned polyester polyol (A) of total, (B) and the number of the hydroxyl that adds up in the monofunctional alcohol (C) than being isocyanate group/hydroxyl=0.5/1.0～1.5/1.0.

＜19〉a kind of non-solvent adhesive composition, it is characterized in that, its second-order transition temperature that contains 5～50 weight % is 10～40 ℃, number-average molecular weight is 500～2000 polyester polyol (A), the second-order transition temperature of 95～50 weight % is-70～0 ℃, number-average molecular weight is 500～2000 polyester polyol (B) (polyester polyol (A) reaches and (B) adds up to 100 weight %), the trifunctional isocyanates compound (D) that forms by alicyclic diisocyanate compound or aromatic diisocyanate compounds, by the trifunctional isocyanates compound (E) of aliphatic diisocyanate compound formation (wherein, above-mentioned trifunctional isocyanates compound (D) and the isocyanate group that (E) adds up to above-mentioned polyester polyol (A) and the number of the hydroxyl that adds up to (B) than being isocyanate group/hydroxyl=0.7/1.0～1.5/1.0) and multi-anhydride (G).

＜20〉a kind of non-solvent adhesive composition, it is characterized in that, it is combined with the second-order transition temperature that contains 5～50 weight % is 10～40 ℃, number-average molecular weight is 500～2000 polyester polyol (A), the second-order transition temperature of 95～50 weight % is-70～0 ℃, number-average molecular weight is the trifunctional isocyanates compound (D) that formed by alicyclic diisocyanate compound or aromatic diisocyanate compounds of the 1st composition of 500～2000 polyester polyol (B) (polyester polyol (A) and (B) add up to 100 weight %) and multi-anhydride (G) and containing and by the 2nd composition of the trifunctional isocyanates compound (E) of aliphatic diisocyanate compound formation, make above-mentioned trifunctional isocyanates compound (D) and (E) in the isocyanate group that adds up to and above-mentioned polyester polyol (A) and (B) in the number of the hydroxyl that adds up to than being isocyanate group/hydroxyl=0.7/1.0～1.5/1.0.

＜21〉a kind of non-solvent adhesive composition, it is characterized in that, its second-order transition temperature that contains 5～50 weight % is 10～40 ℃, number-average molecular weight is 500～2000 polyester polyol (A), the second-order transition temperature of 95～50 weight % is-70～0 ℃, number-average molecular weight is 500～2000 polyester polyol (B) (polyester polyol (A) reaches and (B) adds up to 100 weight %), the trifunctional isocyanates compound (D) that forms by alicyclic diisocyanate compound or aromatic diisocyanate compounds, trifunctional isocyanates compound (E) by the aliphatic diisocyanate compound formation, diisocyanate cpd (F) (wherein, above-mentioned trifunctional isocyanates compound (D), (E) and the isocyanate group that adds up in the vulcabond (F) with above-mentioned polyester polyol (A) and the number of the hydroxyl that adds up to (B) than being isocyanate group/hydroxyl=0.7/1.0～1.5/1.0) and multi-anhydride (G).

＜22〉a kind of non-solvent adhesive composition, it is characterized in that, it is combined with the second-order transition temperature that contains 5～50 weight % is 10～40 ℃, number-average molecular weight is 500～2000 polyester polyol (A), the second-order transition temperature of 95～50 weight % is-70～0 ℃, number-average molecular weight is the 1st composition of 500～2000 polyester polyol (B) (polyester polyol (A) and (B) add up to 100 weight %) and multi-anhydride (G) and contains the trifunctional isocyanates compound (D) that is formed by alicyclic diisocyanate compound or aromatic diisocyanate compounds, trifunctional isocyanates compound (E) by the aliphatic diisocyanate compound formation, the 2nd composition of diisocyanate cpd (F) makes above-mentioned trifunctional isocyanates compound (D), (E) and the isocyanate group that adds up in the diisocyanate cpd (F) with above-mentioned polyester polyol (A) and the number of the hydroxyl that adds up to (B) than being isocyanate group/hydroxyl=0.7/1.0～1.5/1.0.

Embodiment

Below the present invention is described in detail.

At first to being used for non-solvent adhesive composition of the present invention, second-order transition temperature (below be also referred to as Tg) be 10～40 ℃, number-average molecular weight be 500～2000 polyester polyol (A), Tg for-70～0 ℃, number-average molecular weight be that 500～2000 polyester polyol (B) and the monofunctional alcohol (C) that uses in case of necessity describe.Below also polyester polyol (A) is called high Tg polyester polyol (A) sometimes or abbreviates (A) as, polyester polyol (B) is called low Tg polyester polyol (B) or abbreviates (B) as.In addition, also abbreviate monofunctional alcohol (C) as (C) sometimes.

The important point of the present invention is with high Tg polyester polyol (A) and low Tg polyester polyol (B) while and is used as the hydroxyl composition, preferably, further uses monofunctional alcohol (C) in case of necessity.Promptly, add up among the 100 weight % at (A)+(B)+(C), importantly (A): (B): (C)=(5～70): (20～95): (0～30) (weight %), preferred this ratio is (5～70): (20～90): (5～30) (weight %), more preferably this ratio is (30～70): (20～50): (5～30) (weight %).Perhaps do not have and situation with monofunctional alcohol under, preferred (5/95)～(50/50) of weight ratio (A)/(B), more preferably (10/90)～(45/55), preferred especially (15/85)～(40/60).

High Tg polyester polyol (A) is mainly being born the function of guaranteeing tackiness agent force of cohesion.Therefore, from guaranteeing the viewpoint of force of cohesion, the containing ratio of high Tg polyester polyol (A) is improved.But, even and during with the low Tg polyester polyol (B) of relative low melting viscosity, from considering that with the harmony of coating the containing ratio of high Tg polyester polyol (A) is height like that.As the hydroxyl composition, owing to can the containing ratio of high Tg polyester polyol (A) be raise by further also with having the viscosity reduction that more low viscous monofunctional alcohol (C) makes tackiness agent.

In addition, when and with high Tg polyester polyol (A) and low Tg polyester polyol (B) during as the hydroxyl composition since the solidified tackiness agent it is crosslinked overstocked, really up to the mark, so have the tendency of passing bond properties decline after the distillation in time.By further also using monofunctional alcohol (C) as the hydroxyl composition, owing to not only kept the force of cohesion that produces by high Tg polyester polyol (A), and can adjust cross-linking density, therefore, change binding property in time and also can not reduce even after distillation.

But, as described in the background of invention item, tinsel and plastics film fitted and the wrapping material that form have various purposes, therefore require it to have the performance of corresponding purposes respectively.For example, when liquid food during, to carry out various heat treated together with wrapping material sometimes after the filling as content.

Even also do not use monofunctional alcohol (C) as the hydroxyl composition, be solid shape or aqueous for content, particularly after filling content, do not need to carry out the purposes of heat treated, it uses also very desirable as tackiness agent.In addition, even when splendid attire need carry out the aqueous content of heat treated, be not acid content, for example filling resemble congee like this by water and the content state that constitutes of rice under, even distill germicidal treatment, handle between back tinsel and plastics film and also do not peel off.

But through about 1 week, the bounding force between tinsel and plastic film just significantly descends after the distillation.Particularly when fill in the wrapping material be not water but acid content the time, bounding force is passed in time and is reduced more significantly.

When filling acid content, and need carry out heat treated together with wrapping material after filling the time since further and with monofunctional alcohol (C) as the hydroxyl composition, therefore after the distillation As time goes on bond properties do not reduce.

When also not using monofunctional alcohol (C) as the hydroxyl composition, importantly add up among the 100 weight % at (A)+(B), high Tg polyester polyol (A) is more than the 5 weight %, if lack than 5 weight %, then can't obtain sufficient bond properties.

When also using monofunctional alcohol (C) as the hydroxyl composition, add up among the 100 weight % at (A)+(B)+(C), high Tg polyester polyol (A) is preferably more than the 30 weight %.If lack than 30 weight %, then force of cohesion reduces, and exists distillation back bond properties to pass the tendency of reduction in time.

When also not using monofunctional alcohol (C) as the hydroxyl composition, high Tg polyester polyol (A) is preferably below the 50 weight %.In addition, when also using monofunctional alcohol (C) as the hydroxyl composition, importantly high Tg polyester polyol (A) is below the 70 weight %.

When the Tg of high Tg polyester polyol (A) above 40 ℃, number-average molecular weight surpasses 2000, and do not have and during with monofunctional alcohol (C), if more than high Tg polyester polyol (A) the 50 weight %, or when and during with monofunctional alcohol (C), if more than high Tg polyester polyol (A) the 70 weight %, after then cooperating trifunctional isocyanates compound (D), (E) and diisocyanate cpd (F) etc., even be heated to about 70 ℃, the viscosity of binder composition has just surpassed 3000mPas, and coating is suffered damage.

In addition, if the Tg of high Tg polyester polyol (A) is discontented with 10 ℃, number-average molecular weight is discontented with 500, even use the binder composition that makes that plastic film and tinsel etc. are bonding, because the force of cohesion deficiency also can't obtain sufficient bond properties.

In addition, the Tg of high Tg polyester polyol (A) is preferably 20～30 ℃.

If the Tg of low Tg polyester polyol (B) is above 0 ℃, number-average molecular weight surpasses 2000, after cooperating trifunctional isocyanates compound (D), (E) and diisocyanate cpd (F), even be heated to about 70 ℃, the viscosity of binder composition has just surpassed 3000mPas, and coating is suffered damage.

On the other hand, if the Tg of low Tg polyester polyol (B) is discontented with-70 ℃, number-average molecular weight is discontented with 500, even use the binder composition that makes that plastic film and tinsel etc. are bonding, also can't obtain sufficient bond properties.

In addition, the Tg of low Tg polyester polyol (B) is preferably-60～-30 ℃.

In addition, the example of polyester polyol (B) comprises the polyester polyol (B1) that does not contain ehter bond, the polyester polyol (B2) that contains ehter bond.(B2) compares with the polyester polyol that contains ehter bond, and the polyester polyol (B1) that does not contain ehter bond plays the effect of the force of cohesion increase that makes tackiness agent.On the other hand, (B1) compares with the polyester polyol that does not contain ehter bond, and the polyester polyol (B2) that contains ehter bond plays the effect of improving the layered product outward appearance.

According to the formation of purposes, layered product, can be respectively with above-mentioned (B1) and (B2) as polyester polyol (B).

(1) after being used for filling content, in the time of need carrying out the purposes of heat treated together with wrapping material, preferred use does not separately contain the polyester polyol (B1) of ehter bond.Relative therewith, in the formation of layered product, adopt the vapor-deposited film that silicon oxide vapor-deposited film, aluminum oxide vapor-deposited film etc. can heat treated, with adhesive coated to these evaporation faces, during with other base material laminations, bad order sometimes.In this case, preferably will contain the polyester polyol (B2) of ehter bond and not contain the polyester polyol (B1) and the usefulness of ehter bond, or use the polyester polyol (B2) that contains ehter bond separately.

(2) after being used for filling content, when not needing to carry out the purposes of heat treated, preferably, use above-mentioned (B1) and (B2) respectively according to the formation of layered product together with wrapping material.In the formation of layered product, adopt vapor-deposited films such as aluminium-vapour deposition film, silica steam plating film, aluminum oxide vapor-deposited film, with adhesive coated to these evaporation faces, during with other base material laminations, the preferred polyester polyol (B2) that contains ehter bond that uses separately, or be must composition, and then and with the polyester polyol (B2) that contains ehter bond with the polyester polyol (B1) that does not contain ehter bond.

Below the formation of layered product and the relation that is suitable between the end article outward appearance of binder composition of the present invention are described.

With plastic film and tinsel, or plastic film and evaporation the evaporation face of vapor-deposited film of aluminium, aluminum oxide or silicon oxide etc. fit and the layered product that forms, it can be used as wrapping material.These wrapping material generally use " the inside printing " overlay to be provided with printed layers.So-called " the inside printing " be meant passing through overlay, see under the prerequisite of printed layers from the one side (surface) of overlay, at the another side (the inside) of overlay printed layers is set.So between the evaporation face of printed layers and tinsel or vapor-deposited film, binder layer is set,, makes the layered product that it constitutes overlay/printed layers/binder layer/(tinsel or vapor-deposited film) with plastic film and tinsel or vapor-deposited film lamination.

In this case, the printed layers of She Zhiing for convenience, its (outward appearance) attractive in appearance is used in force of cohesion aspect excellence afterwards, do not contain the tackiness agent infringement that the polyester polyol (B1) of ehter bond forms.That is, if the binder layer that uses polyester polyol (B1) to constitute is set, then produce tiny, random mottled deep or lightly sometimes on printed layers, it can be seen by plastic film.Detailed reason is still indeterminate, if but use the polyester polyol (B2) that contains ehter bond as polyester polyol (B), then can eliminate this bad order.

Therefore, when after filling content, heat-treating together with wrapping material, and when requiring to have higher bond properties, preferably, will not contain the polyester polyol (B1) of ehter bond and contain the polyester polyol (B2) of ehter bond and be used as polyester polyol (B).On the other hand, when after filling content, not needing to heat-treat, consider that from the outward appearance aspect of layered product preferred the use separately contained the polyester polyol (B2) of ehter bond as polyester polyol (B) together with wrapping material.

In addition, when the polyester polyol (B1) that will not contain ehter bond with contain the polyester polyol (B2) and the time spent of ehter bond, preferred (B1)/(B2)=1～99/99～1 (weight ratio), more preferably 90～10/10～90 (weight ratios).

As polyester polyol of the present invention (A) or (B), can use diprotic acid or their dialkyl and multi-anhydride or their mixture and polyalcohols to react and the polyester polyol that obtains or polycaprolactone, poly-valerolactone, poly-lactone such as (Beta-methyl-γ-Wu Neizhis) are carried out the polyester polyol that ring-opening polymerization obtains.

In polyester polyol (B), do not contain the polyester polyol (B1) of ehter bond and contain the polyester polyol (B2) of ehter bond can be respectively by using the polyalcohols that does not contain the polyalcohols of ehter bond and contain ehter bond to make.

As diprotic acid or their dialkyl, it comprises diprotic acid such as terephthalic acid, m-phthalic acid, hexanodioic acid, nonane diacid, sebacic acid, fumaric acid, methylene-succinic acid or their dialkyl etc.

As multi-anhydride, it such as comprises at trimellitic acid 1,2-anhydride, tetrahydrotoluene tricarboxylic acid anhydride, pyromellitic acid acid anhydride etc.

In addition, operable polyalcohols is as described below.

At first, the polyalcohols that does not contain ehter bond that uses when not containing the polyester polyol (B1) of ehter bond as preparation, it comprises ethylene glycol, propylene glycol, butyleneglycol, neopentyl glycol, 1,6-hexylene glycol, 3-methyl isophthalic acid, 5-pentanediol, butyl ethyl propylene glycol, 1,9-nonanediol, decamethylene-glycol, 3, di-alcoholss such as 3 '-dihydroxymethyl heptane; Trivalent alcohols such as glycerine, trimethylolethane, TriMethylolPropane(TMP); Tetravalent alcohol such as tetramethylolmethane, Dipentaerythritol etc.Other also comprise the vinylcarbinol multipolymer (Network イ Application ト Application 1700 (trade(brand)names) of for example Japanese ゼ オ Application (strain) system) of rosiny alcohol derivate (KE-601 (trade(brand)name) of for example waste river chemistry (strain) system), cyclopentadiene.

On the other hand, the polyalcohols that contains ehter bond that uses when containing the polyester polyol (B2) of ehter bond as preparation, it comprises the di-alcoholss such as multipolymer, polytetramethylene glycol of Diethylene Glycol, dipropylene glycol, triethylene glycol, polyoxyethylene glycol, polyoxypropylene glycol, oxyethane and propylene oxide.

Monofunctional alcohol (C) plays the effect of reactive diluent before curing, play the effect of adjusting cross-linking density during curing and after solidifying.

From guaranteeing the viewpoint of force of cohesion, preferably improve the containing ratio of high Tg polyester polyol (A).But, even and during with the low Tg polyester polyol (B) of relative low melting viscosity, from considering that with the harmony of coating the containing ratio of high Tg polyester polyol (A) is height like that.Owing to also with having more low viscous monofunctional alcohol (C), the viscosity of tackiness agent is reduced by further, therefore can improve the containing ratio of high Tg polyester polyol (A) as the hydroxyl composition.

In addition, produced so far since the solidified tackiness agent it is crosslinked overstocked, really up to the mark, the problem that therefore has and pass in time after the distillation (through time) bond properties to reduce.But,, therefore pass bond properties in time after the distillation and no longer reduce owing to, not only can keep the force of cohesion that produces by high Tg polyester polyol (A), and can adjust cross-linking density by further also using monofunctional alcohol (C) as the hydroxyl composition.

As the preferred monofunctional alcohol (C) that uses among the present invention, its molecular weight is generally more than 100, and is preferred more than 150, below 1000,20 ℃ viscosity is generally below the 50mPas, below the preferred 20mPas, more than the 0.1mPas, boiling point is generally more than 150 ℃, preferred more than 200 ℃, below 350 ℃, 20 ℃ vapour pressure is generally below the 10mmHg, below the preferred 1mmHg, more than the 0.0001mmHg.

Concrete example as this monofunctional alcohol (C), lauryl alcohol), n-tetradecanol, 2-ethyl-alkyl alcohols such as 1-hexanol it comprises nonylcarbinol, n-dodecane alcohol (another name:, ethylene glycol monoalkyl ether such as ethylene glycol monobutyl ether, ethylene glycol ether, Diethylene Glycol monoalky lethers such as propylene-glycol monoalky lether, Diethylene Glycol single 2-ethyl hexyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether etc.Preferred n-dodecane alcohol, 2-ethyl-1-hexanol, Diethylene Glycol single 2-ethyl hexyl ether.

Non-solvent adhesive composition of the present invention, as described later, after cooperating polyester polyol (A), (B), monofunctional alcohol (C) and trifunctional isocyanates compound (D), (E), vulcabond (F) etc. under the heating, under softening or molten state, will be applied on the flat substrates.During coating, if the reaction of polyester polyol (A), (B), monofunctional alcohol (C) and trifunctional isocyanates compound (D), (E), diisocyanate cpd (F) etc. is being carried out, then viscosity raises, and brings obstruction for coating itself.

Therefore, polyester polyol (A), (B), monofunctional alcohol (C) and trifunctional isocyanates compound (D), (E), diisocyanate cpd (F) etc. preferably do not react as far as possible during coating.

When synthesizing polyester type polyvalent alcohol (A), (B), can use esterifying catalyst.

But esterifying catalyst also can become the hydroxyl in polyester polyol (A), (B) and the monofunctional alcohol (C) and the catalysts of the isocyanate group in trifunctional isocyanates compound (D), (E) and the diisocyanate cpd (F) sometimes.Therefore, for when being applied to binder composition on the flat substrates, polyester polyol (A), (B), monofunctional alcohol (C) and trifunctional isocyanates compound (D), (E) and diisocyanate cpd (F) do not react as far as possible, when synthesizing polyester type polyvalent alcohol (A), (B), preferably do not use this esterifying catalyst.

In addition, if remaining in polyester polyol (A), (B) have carboxyl, just this carboxyl becomes the catalyzer of polyester polyol (A), (B), monofunctional alcohol (C) and trifunctional isocyanates compound (D), (E) and diisocyanate cpd (F).Therefore, for above-mentioned same reason, the amount of carboxyl is few more good more in the polyester polyol (A), (B).

The amount of this carboxyl can be represented with acid number.Below preferred 5 (mgKOH/g) of the acid number of polyester polyol (A), (B), more preferably below 2.5 (mgKOH/g), most preferably below 1 (mgKOH/g), more than 0.01 (mgKOH/g).

Below employed two kinds of trifunctional isocyanates compounds (D), (E) and diisocyanate cpd (F) among the present invention are described.Below abbreviate trifunctional isocyanates compound (D), (E) and diisocyanate cpd (F) as (D), (E) and (F) sometimes respectively.

Isocyanate compound (D), (E) and diisocyanate cpd (F), as described later, with after above-mentioned polyester polyol (A), (B), monofunctional alcohol (C) etc. mix, be applied on the flat substrates, at other flat substrates of heating laminated, thereby make polyester polyol (A), (B), monofunctional alcohol (C) reaction, between two flat substrates, form binder layer.

Isocyanate compound (D), (E) are the trifunctional isocyanates compound, are the materials that is formed by diisocyanate cpd.In addition, diisocyanate cpd (F) is alicyclic, aromatic series, aliphatic various known various diisocyanates.They are respectively the materials with ad hoc structure as follows.The invention is characterized in: isocyanate compound (D) is reached (E) both and usefulness, or isocyanate compound (D) is reached (E), and then and diisocyanate cpd (F) three and usefulness.

As diisocyanate cpd, it comprises alicyclic, aromatic series, aliphatic various known various diisocyanates.

For example, alicyclic diisocyanate comprises hexanaphthene-1,4-vulcabond, isophorone diisocyanate, dicyclohexyl methyl hydride-4,4 '-vulcabond, 1,3-two (isocyanic ester methyl) hexanaphthene, methylcyclohexane diisocyanate, norbornene alkyl diisocyanate etc.

Aromatic diisocyanate comprises 1,5-naphthalene diisocyanate, 4,4 '-'-diphenylmethane diisocyanate, 4,4 '-phenylbenzene dimethylmethane vulcabond, 4,4 '-dibenzyl vulcabond, dialkyl group diphenylmethanediisocyanate, tetraalkyl diphenylmethanediisocyanate, phenylene-1,3-vulcabond, 1,4-phenylene vulcabond, methylene phenylene diisocyanate, xylylene diisocyanate etc.

Aliphatic diisocyanate comprises butane-1,4-vulcabond, hexamethylene diisocyanate, pseudoallyl vulcabond, methylene diisocyanate, 2,2, the 4-trimethyl hexamethylene diisocyanate ,-tetramethyl xylylene diisocyanate, lysinediisocyanate (リ ジ Application ジ イ ソ シ ア ネ-ト), be converted into dimerization vulcabond of isocyanate group etc. with the carboxyl of dimeracid.

Can make the isocyanate compounds more than the trifunctional such as affixture as follows, isocyanuric acid ester, biuret by above-mentioned diisocyanate cpd.

Affixture makes by making the reaction of various known various diisocyanate cpds and the alcohol more than the ternary.Situation when being to use trifunctional alcohol shown below.

Affixture

In the formula, R is an isocyanate group residue in addition of removing diisocyanates.

P is a hydroxyl residue in addition of removing trifunctional alcohol.

As the alcohol more than the ternary that is used for affixture, it comprises glycerine, TriMethylolPropane(TMP), trimethylolethane, 1,2,6-hexanetriol, 1,2,4-trihydroxybutane, sorbyl alcohol, tetramethylolmethane etc.

Be shown below, isocyanuric acid ester is made of various known various diisocyanate cpd 3 molecules.

Isocyanuric acid ester

In the formula, R is an isocyanate group residue in addition of removing diisocyanates.

Be shown below, biuret is reacted by various known various diisocyanate cpds and water and makes.

Biuret

In the formula, R is an isocyanate group residue in addition of removing diisocyanates.

Trifunctional isocyanates compound (D) is served as reasons and is had the diisocyanate cpd of ring texture, promptly by affixture, isocyanuric acid ester or biuret alicyclic or that aromatic diisocyanate compounds forms, and preferred isocyanuric acid ester.

Preferred especially Trimerization of Isophorone Diisocyanate isocyanic ester.

Trifunctional isocyanates compound (E) is served as reasons and is not had the diisocyanate cpd of ring texture, i.e. the affixture of aliphatic diisocyanate compound formation, isocyanuric acid ester or biuret, preferably isocyanuric acid ester or biuret.

Preferred especially 1, the isocyanuric acid ester of 6-HDI or biuret, most preferably 1, the biuret of 6-HDI.

As diisocyanate cpd (F), it comprises above-mentioned alicyclic, aromatic series, aliphatic various known various diisocyanates, preferred alicyclic diisocyanate, aromatic diisocyanate, preferred especially isophorone diisocyanate.

In the present invention, importantly trifunctional isocyanates compound (D) is reached (E) and usefulness, or on trifunctional isocyanates compound (D) and basis (E), further also use diisocyanate cpd (F).

(E) compares with the trifunctional isocyanates compound, because the ring structure of trifunctional isocyanates compound (D), so the viscosity during its fusion is big.Therefore, if only use the trifunctional isocyanates compound (D) contain ring structure, then the viscosity during the binder composition fusion increases, the coating difficulty that becomes.

If only use the isocyanate compound (E) of trifunctional, then can not obtain sufficient bond properties.

If only use diisocyanate cpd (F), when then printing on flat substrates, diisocyanate cpd (F) becomes the reason of bond properties inequality easily by absorption of inks, is worthless therefore.In addition, if only use diisocyanate cpd (F), also be worthless aspect health.

Therefore, importantly by both also use with trifunctional isocyanates compound (D) and (E), or with trifunctional isocyanates compound (D), (E) and diisocyanate cpd (F) three and usefulness, the harmony of viscosity and bond properties when obtaining the binder composition fusion.

And during with (F), in the 100 weight % that (D)+(E)+(F) adds up to, (D): (E): weight ratio (F) preferred (5～70): (20～90): (1～70), further preferred (10～70): (25～80): (5～60), preferred (15～60) especially: (30～70): (5～50).Perhaps when not having and during preferred (5/95)～(70/30) of weight ratio (D)/(E), further preferred (10/90)～(65/35), preferred especially (15/85)～(60/40) with (F).

And then in the present invention, except above-mentioned trifunctional isocyanates compound (D), (E) and diisocyanate cpd (F), can also use triphenyl methane-4,4 '; 4 "-triisocyanate, 1,3,5-three phenylcarbimides, 2,4,6-three isocyanide toluylates, 4,4 '-dimethyl diphenylmethane-2,2 ', 5,5 "-tetraisocyanate etc. contains the isocyanate compound of 3 above isocyanate group.

Binder composition importantly of the present invention contains multi-anhydride (G).Owing to contain multi-anhydride (G), it is hereby ensured the binding property of aluminium etc. and plastic film.

In the present invention, multi-anhydride can use Tetra hydro Phthalic anhydride as the acid anhydrides of polyprotonic acids such as phthalic acid, trimellitic acid, pyromellitic acid for example, trimellitic acid 1,2-anhydride, pyromellitic acid acid anhydride etc.

In these acid anhydrides, preferred especially trimellitate acid anhydride.

The trimellitate acid anhydride comprises three dehydration trimellitic acid glycerine esters shown in the two dehydration trimellitic acid glycol esters shown in the following formula (1), the following formula (2) etc., the more preferably two dehydration trimellitic acid glycol esters shown in the following formula (1).

These acid anhydrides can be buied by new Japanese physics and chemistry (strain), and its commodity are called リ カ シ Star De TMA-X (wherein X is 0 or 10, reaches 15), リ カ シ Star De TMEG-X (wherein X is 100,200,500,600) (each trade(brand)name).

As multi-anhydride (G), can also use derivative that maleic anhydride is carried out addition reaction and generate in sylvic acid, petroleum resin and their mixture of rosin composition etc.

Non-solvent adhesive composition of the present invention can make by the whole bag of tricks for example shown below, the method for preferred (3).

(1) polyester polyol (A), (B), monofunctional alcohol (C), trifunctional isocyanates compound (D), (E), diisocyanate cpd (F) and multi-anhydride (G) are mixed.

(2) preparation mixes polyester polyol (A), (B), monofunctional alcohol (C) and multi-anhydride (G) and the 1st composition of formation, mixes trifunctional isocyanates compound (D), (E), diisocyanate cpd (F) subsequently in the 1st composition.

(3) preparation mixes polyester polyol (A), (B), monofunctional alcohol (C) and multi-anhydride (G) and the 1st composition of formation, prepare the mixture (the 2nd composition) of trifunctional isocyanates compound (D), (E) and diisocyanate cpd (F) in addition, subsequently two compositions are mixed.

In addition, when carrying out the method for (2), (3), mix trifunctional isocyanates compound (D), (E), (F) is preceding for diisocyanate cpd, or before mixing the 2nd composition, the hydroxyl part of the polyester polyol in the 1st composition (A), (B), monofunctional alcohol (C) can with part or all reaction of multi-anhydride (G).

Address in the following explanation last, for convenience's sake, mentioned monofunctional alcohol (C) and diisocyanate cpd (F) and be illustrated, but in the present invention, do not used monofunctional alcohol (C) and/or diisocyanate cpd (F) sometimes according to the difference of forming.

Binder composition of the present invention, the number of the summation of the middle hydroxyl of the summation of isocyanate group and above-mentioned polyester polyol (A), (B) and monofunctional alcohol (C) is than being isocyanate group/hydroxyl=0.5/1.0～2.0/1.0 in its trifunctional isocyanates compound (D), (E) and the diisocyanate cpd (F), preferred 0.5/1.0～1.5/1.0, more preferably 0.7/1.0～1.5/1.0, most preferably 0.7/1.0～1.3/1.0.

Compare with hydroxyl,, then can become and solidify bad reason if isocyanate group is less relatively.

On the other hand, if compare with hydroxyl, isocyanate group is too much relatively, then mix before back, the coating or in the coating process hydroxyl carry out too much with the reaction of isocyanate group, it is difficult that coating itself becomes.In addition, if isocyanate group is too much relatively, the price of binder composition raises, and is disadvantageous economically.And also be worthless aspect health.

Binder composition of the present invention for the polyester polyol (A), (B) and the monofunctional alcohol (C) that add up to 100 weight parts, can use the multi-anhydride (G) of 0.1～2 weight part.If the multi-anhydride (G) that uses is very few, then can't obtain enough bounding forces.On the other hand, if too much, then when polyester polyol of the present invention etc. and isocyanate compound etc. mixed, because reaction is quickened, the viscosity increase was remarkable, is worthless in operation.And then also can be unfavorable on cost.Preferably, can in the scope of 0.2～1 weight part, use multi-anhydride (G).

Non-solvent adhesive composition of the present invention can also contain the oxygen acid or derivatives thereof (H) of phosphorus, for the polyester polyol (A), (B) and the monofunctional alcohol (C) that add up to 100 weight parts, preferably contain 0.01～5 weight part, more preferably contain 0.02～1 weight part.

Owing to contain the oxygen acid or derivatives thereof of phosphorus, so acid resistance improves.

Oxygen acid as phosphorus, can be any material that contains at least more than one free oxygen acid, it comprises for example phosphoric acid classes such as Hypophosporous Acid, 50, phosphorous acid, ortho-phosphoric acid, diphosphanetetroic acid, condensed phosphoric acid classes such as metaphosphoric acid, tetra-sodium, tripolyphosphate, polyphosphoric acid, peroxophosphoric acid.

As the derivative of the oxygen acid of phosphorus, it is included in remaining at least more than 1 under the state of free oxygen acid, makes the oxygen acid of above-mentioned phosphorus and alcohols partial esterification and the material that obtains.These alcohol comprise aromatic alcohols such as Fatty Alcohol(C12-C14 and C12-C18) such as methyl alcohol, ethanol, ethylene glycol, glycerine, phenol, xylenol, Resorcinol, catechol, Phloroglucinol etc.The oxygen acid or derivatives thereof of phosphorus may be used singly or two or more kinds thereof.

When containing the oxygen acid or derivatives thereof (H) of phosphorus, non-solvent adhesive composition of the present invention can make by the whole bag of tricks for example shown below, the method for preferred (3).

(1) the oxygen acid or derivatives thereof (H) with polyester polyol (A), (B), monofunctional alcohol (C), trifunctional isocyanates compound (D), (E), diisocyanate cpd (F), multi-anhydride (G) and phosphorus mixes.

(2) preparation mixes the oxygen acid or derivatives thereof (H) of polyester polyol (A), (B), monofunctional alcohol (C), multi-anhydride (G) and phosphorus and the 1st composition of formation, mixes trifunctional isocyanates compound (D), (E), diisocyanate cpd (F) subsequently in the 1st composition.

(3) preparation mixes the oxygen acid or derivatives thereof (H) of polyester polyol (A), (B), monofunctional alcohol (C), multi-anhydride (G) and phosphorus and the 1st composition of formation, prepare the mixture (the 2nd composition) of trifunctional isocyanates compound (D), (E) and diisocyanate cpd (F) in addition, subsequently two compositions are mixed.

In addition, when carrying out the method for (2), (3), mix trifunctional isocyanates compound (D), (E), (F) is preceding for diisocyanate cpd, or before mixing the 2nd composition, the part of the hydroxyl composition in the 1st composition can with part or all reaction of the oxygen acid or derivatives thereof (H) of multi-anhydride (G) or phosphorus.

In non-solvent adhesive composition of the present invention, can also use adhesion promotor.

Adhesion promotor comprises that silane coupling agent, titanic acid ester are coupling agent, Resins, epoxy such as coupling agent, aluminium system.

Silane coupling agent comprises γ-An Jibingjisanyiyangjiguiwan, gamma-amino propyl trimethoxy silicane, N-β (aminoethyl)-gamma-amino propyl trimethoxy silicane, N-β (aminoethyl)-gamma-amino oxypropyl trimethyl dimethoxy silane, N-phenyl-aminosilanes such as gamma-amino propyl trimethoxy silicane; The epoxy silane of β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxy propyl-triethoxysilicane; Vinyl three ('beta '-methoxy oxyethyl group) silane, vinyltriethoxysilane, vinyltrimethoxy silane, γ-vinyl silanes such as (methacryloxy) propyl trimethoxy silicane; Hexamethyldisilane, γ-Qiu Jibingjisanjiayangjiguiwan etc.

Titanic acid ester is that coupling agent comprises for example tetraisopropoxy titanium, four titanium n-butoxide, butyl (tetra) titanate dimer, metatitanic acid four (octadecyl) ester, titanium acetylacetone, lactic acid titanium, metatitanic acid four ethohexadiol esters, lactic acid titanium, four stearic oxygen base titaniums etc.

In addition, aluminium is that coupling agent comprises for example acetyl alkoxyl group aluminum-diisopropoxide etc.

Resins, epoxy comprises various Resins, epoxy such as common Epicholorohydrin-bisphenol A-type of selling, phenol aldehyde type, Beta-methyl table chlorine type, ring-type ethylene oxide type, glycidyl ether type, glycidic ester type, polyglycol ether type, glycol ether type, epoxidized fatty acid ester type, multi-carboxylate's type, amino Racemic glycidol type, Resorcinol type on the market.

Except mentioned component, can also in non-solvent adhesive composition of the present invention, use weighting agent, tenderizer, anti-aging agent, stablizer, adhesion promotor, flow agent, defoamer, softening agent, mineral filler, bonding giving property resin, fiber-like, serviceable time to prolong agent, antioxidant, UV light absorber in case of necessity, add water decomposition and prevent known various additives such as tinting material, weighting agent such as agent, anti-microbial inoculum, tackifier, softening agent, pigment.In addition, can use the known catalysts that is used to regulate curing reaction, additive etc.

Below sheet material that has binder layer and the manufacture method thereof of using above-mentioned non-solvent adhesive composition to form described.

Make the non-solvent adhesive composition that contains polyester polyol (A), (B), monofunctional alcohol (C), trifunctional isocyanates compound (D), (E), diisocyanate cpd (F) and multi-anhydride (G), under heating, this binder composition is applied on the face of various flat substrates, thereby has formed the sheet material that has binder layer of the present invention.

For the non-solvent adhesive composition is applied on the flat substrates, can be extensive use of present known method.For example use the membrane layer mode of rubber rollers or metallic roll etc.The manner is adjusted adhesive spread by pressure and peripheral speed difference between the roller of coating roll.

The sheet material that has binder layer that makes, the reaction of its binder layer polyester polyol (A), (B) and monofunctional alcohol (C) and trifunctional isocyanates compound (D), (E) and diisocyanate cpd (F) should not terminate.If in this elementary reaction termination, can't other flat substrates of lamination in following step, therefore can carry out a reaction, reaction should not terminate.

Preferred 0.1～10 μ m of coating thickness (and then preferred 0.1～5 μ m), the preferred 0.1～5g/m of glue spread ²

Preferably, consider the operation in when coating and the heating viscosity of non-solvent adhesive composition down, usually the non-solvent adhesive composition is heated to room temperature～120 ℃, preferably be heated to 40～100 ℃.

In addition, from guaranteeing the activity duration consideration, with polyester polyol (A), (B), monofunctional alcohol (C), trifunctional isocyanates compound (D), (E), diisocyanate cpd (F), and after multi-anhydride (G) mixes, preferably, non-solvent adhesive composition of the present invention is below the 20000mPas through the viscosity under 30 minutes post-heating, more preferably, viscosity under 60 minutes post-heating is below the 20000mPas, further preferably, the viscosity under 60 minutes post-heating is below the 10000mPas.

As the material of above-mentioned flat substrates, it for example comprises polyoses such as tinsel class, stationery, glass stationery, osso-albumin etc. are protein-based, amylopectin, polyolefins, polyvinyl chloride, polyvinylidene chloride class, polystyrene type, polyvinyl alcohol, polyacrylonitrile class, fluorine based polymer, polyester, polycarbonate-based, polyamide-based, polyurethanes, polysulfones, polyetherimides, vapor-deposited film etc.In the present invention, also can use not stretching flat substrates or the stretching flat substrates that forms by these materials as flat substrates.

In addition, in the present invention, can also use the compound sheet base material that a plurality of flat substrates that formed by above-mentioned various materials is carried out lamination and form.

The tinsel class comprises aluminium foil, iron foil, lead foil, tinfoil paper etc.

Stationery comprises pure white paper, vellum, enamelled paper, kraft paper, cardboard, rayon paper, mixed copy paper, non-woven paper etc.

The glass stationery comprises simple glass paper, damp proof glassine paper (varnish coating, polymeric coating, polyethylene coating) etc.

Polyolefins comprises nonpolar polyolefin hydro carbons, polar polyolefin class.

The nonpolar polyolefin hydro carbons comprises new LDPE (film grade), medium-density polyethylene, high density polyethylene(HDPE), ethylene-vinyl acetate copolymer, chlorinatedpolyethylene, polypropylene, propylene-ethylene random copolymers, propylene-ethylene block copolymer, propene-1-butene copolymer, propylene-ethylene-butene multipolymer, polybutene-1,2-polyhutadiene etc.

In addition, the polar polyolefin class comprises ethylene-methyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, iolon etc.

Polyvinyl chloride comprises thermoplastic polyvinyl chloride, rigid polyvinyl chloride, semi-rigid polyvinyl chloride, soft PVC etc.

The polyvinylidene chloride class comprises vinylidene chloride-acrylonitrile copolymer, vinylidene chloride-vinyl chloride copolymer, vinylidene chloride-Sipacril 2739OF etc.

Polystyrene type comprises polystyrene, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer etc.

Polyvinyl alcohol comprises non-plasticity-polyvinyl alcohol, plasticity-polyvinyl alcohol, saponification ethylene-vinyl acetate copolymer etc.

The polyacrylonitrile class comprises Acrylonitrile metry1 methacrylate copolymer.Deng

Fluoro-resin comprises tetrafluoraoethylene-hexafluoropropylene copolymer, trifluoro-ethylene-vinyl chloride copolymer etc.

Polyester comprises polyethylene terephthalate, 1,4-cyclohexylidene dimethylene terephthalate/isophthalic acid ester etc.

Polycarbonate-based polycarbonate, the poly phthalate carbonic ether etc. of comprising.

Polyamide-based nylon 6, nylon 66, the xylylene diamine-amide copolymer etc. of comprising.

Vapor-deposited film comprises the opaque vapor-deposited film of transparent vapor-deposited films such as silicon oxide vapor-deposited film, aluminum oxide vapor-deposited film, aluminium-vapour deposition film and so on etc.In addition, base material is polyester film (PET), un-stretched polypropylene film (CPP), stretched polypropene film (OPP), oriented nylon film (ONY), polyethylene film (PE), rigid polyvinyl chloride film (hard PVC), polycarbonate film (PC) etc., the base material of aluminium-vapour deposition preferably uses PET, ONY, OPP, CPP etc., and the base material of silicon oxide evaporation, aluminum oxide evaporation preferably uses PET etc.

Preferable alloy paper tinsel, polyolefins, polyester, vapor-deposited film class, the preferred aluminium of tinsel, the polyolefins optimization polypropylene, the preferred polyethylene terephthalate of polyester, the preferred aluminium-vapour deposition polypropylene screen of vapor-deposited film class, silicon oxide evaporation polyester film, aluminum oxide evaporation polyester film.

Below the sheet layered product that uses the above-mentioned sheet material that has a binder layer to form is described.

As mentioned above, have the sheet material of binder layer, the reaction between the hydroxyl of its binder layer and isocyanate group or hydroxyl and the multi-anhydride is termination not.Therefore, when other flat substrates are contacted on this binder layer, owing to, therefore can make the sheet layered product in that the binder layer reaction is carried out.

When other flat substrates are contacted on binder layer, preferably under heating, make its contact, and then preferably make its contact adding to depress.Particularly, preferably use nip rolls.

In addition, crosslinked in order to promote, preferred sheet layered product wears out under 30～50 ℃ of temperature.

Composition of the present invention is between plastic films such as the tinsel of for example aluminium and so on and polyethylene terephthalate, polypropylene, polyester, nylon, polyethylene or between plastic films such as vapor-deposited film and nylon, demonstrate extremely excellent bounding force, hot water resistance, be filled under the wrapping material state or (for example at Jiang Shui with acidic liquid, 1: 1: 1 described later soup compound) is filled under the wrapping material state, even under 120 ℃, distill germicidal treatment, do not peel off between tinsel and plastic film, can make the wrapping material that the food prolonged preservation has good stability.

Below in conjunction with embodiment the present invention is specifically described, but the present invention is not limited to these embodiment.

Embodiment

The number-average molecular weight of polyester polyol is tried to achieve with gel permeation chromatography (GPC), is counted as the polystyrene standard scaled value.The vitrifying tansition temperature of polyester polyol (the following Tg that is designated as sometimes) is tried to achieve under atmospheric pressure with difference formula scanning calorimeter (DSC).Brookfield viscometer is used in viscosimetric analysis behind cooperation polyester polyol and the polyisocyanate compounds.

" part " of below mentioning is all expressions " weight part " if no special instructions.

(synthesis example 1)

With 438 parts of m-phthalic acids, 106 parts of ethylene glycol, 179 parts of neopentyl glycol reaction vessel of packing into, under stream of nitrogen gas, be heated to 150 ℃～240 ℃ while stirring, carry out esterification.When acid number reaches 1.3, temperature of reaction is reduced to 200 ℃, reaction vessel is slowly carried out step-down, below 10mmHg, make its reaction 30 minutes, make acid number and be 0.4, number-average molecular weight is that about 800, Tg is the polyester polyol resin that two about 27 ℃ ends contain hydroxyl.Below this resin note is made polyester polyol A-1.

(synthesis example 2)

With 415 parts of m-phthalic acids, 109 parts of ethylene glycol, 182 parts of neopentyl glycol reaction vessel of packing into, under stream of nitrogen gas, be heated to 150 ℃～240 ℃ while stirring, carry out esterification.When acid number reaches 1.3, temperature of reaction is reduced to 200 ℃, reaction vessel is slowly carried out step-down, below 10mmHg, make its reaction 30 minutes, make acid number and be 0.5, number-average molecular weight is that about 600, Tg is the polyester polyol resin that two about 16 ℃ ends contain hydroxyl.Below this resin note is made polyester polyol A-2.

(synthesis example 3)

With 310 parts of cis-1,4 cyclohexanedicarboxylic acids, 415 parts of 1,4 cyclohexane dimethanols reaction vessel of packing into, under stream of nitrogen gas, be heated to 150 ℃～220 ℃ while stirring, carry out esterification.When acid number reaches 3.0, temperature of reaction is reduced to 200 ℃, reaction vessel is slowly carried out step-down, below 10mmHg, make its reaction 30 minutes, make acid number and be 2.0, number-average molecular weight is that about 390, Tg is the polyester polyol resin that two about 32 ℃ ends contain hydroxyl.Below this resin note is made polyester polyol A-3.

(synthesis example 4)

With 187 parts of m-phthalic acids, 278 parts of sebacic acid, 56 parts of ethylene glycol, 283 parts of neopentyl glycol reaction vessel of packing into, under stream of nitrogen gas, be heated to 150 ℃～240 ℃ while stirring, carry out esterification.When acid number reaches 0.5, temperature of reaction is reduced to 200 ℃, reaction vessel is slowly carried out step-down, below 10mmHg, make its reaction 30 minutes, make acid number and be 0.06, to be about 1000, Tg contain the polyester polyol resin of hydroxyl for-50 ℃ two ends approximately to number-average molecular weight.Below this resin note is made polyester polyol B-1.

(synthesis example 5)

With 100 parts of polyester polyol B-1,1.5 parts of isophorone diisocyanates (the following IPDI that is abbreviated as sometimes) reaction vessel of packing into, under stream of nitrogen gas, be heated to 90 ℃～100 ℃ while stirring, the absorption of carrying out polyurethane-reinforcement reaction isocyanic ester in infrared spectroscopic analysis disappears, and makes number-average molecular weight and is about 1050, Tg and contain the polyester polyol resin of hydroxyl for-50 ℃ two ends approximately.Below this resin note is made polyester polyol B-2.

(synthesis example 6)

With 224 parts of m-phthalic acids, 333 parts of sebacic acid, 51 parts of ethylene glycol, 257 parts of neopentyl glycol reaction vessel of packing into, under stream of nitrogen gas, be heated to 150 ℃～240 ℃ while stirring, carry out esterification.When acid number reaches 3.1, temperature of reaction is reduced to 200 ℃, reaction vessel is slowly carried out step-down, below 10mmHg, make its reaction 30 minutes, make acid number and be 2.0, to be about 6000, Tg contain the polyester polyol resin of hydroxyl for-28 ℃ two ends approximately to number-average molecular weight.Below this resin note is made polyester polyol B-3.

(synthesis example 7)

With 344 parts of cis-1,4 cyclohexanedicarboxylic acids, 304 parts of propylene glycol reaction vessel of packing into, under stream of nitrogen gas, be heated to 150 ℃～220 ℃ while stirring, carry out esterification.When acid number reaches 0.6, temperature of reaction is reduced to 200 ℃, reaction vessel is slowly carried out step-down, below 10mmHg, make its reaction 30 minutes, make acid number and be 0.3, to be about 450, Tg contain the polyester polyol resin of hydroxyl for-26 ℃ two ends approximately to number-average molecular weight.Below this resin note is made polyester polyol B-4.

(synthesis example 8)

30 parts of デ グ サ ジ ヤ パ Application (strain) systems VESTANATT1890/100 (isocyanuric acid ester of trade(brand)name, IPDI) and 70 parts are firmly changed バ イ エ Le ウ レ Application (strain) make ス ミ ジ ユ one Le N3200 (trade(brand)name, 1, the biuret of 6-HDI (the following HDI that is abbreviated as sometimes)) reaction vessel of packing into, under stream of nitrogen gas, heated 30～60 minutes down at 100 ℃～120 ℃ while stirring, dissolve.The polyisocyanate compounds 1 of this product as embodiment used.

(synthesis example 9)

With 201 parts of m-phthalic acids, 217 parts of hexanodioic acids, 61 parts of ethylene glycol, 265 parts of neopentyl glycol, 59 parts of triglycols reaction vessel of packing into, under stream of nitrogen gas, be heated to 150 ℃～240 ℃ while stirring, carry out esterification.When acid number reaches 1.4, temperature of reaction is reduced to 200 ℃, reaction vessel is slowly carried out step-down, below 10mmHg, make its reaction 30 minutes, make acid number and be 1.0, to be about 1500, Tg contain the polyester polyol resin of hydroxyl for-55 ℃ two ends approximately to number-average molecular weight.Below this resin note is made polyester polyol B-5.

(synthesis example 10)

Biuret with 50 parts of デ グ サ ジ ヤ パ Application (strain) systems VESTANATT1890/100 (isocyanuric acid ester of trade(brand)name, IPDI), 30 parts of HDI), 20 parts of isophorone diisocyanates reaction vessel of packing into, under stream of nitrogen gas, heated 30～60 minutes down at 100 ℃～120 ℃ while stirring, dissolve.The polyisocyanate compounds 2 of this product as embodiment used.

(embodiment 1-1)

In 40 parts of polyester polyol A-1,40 parts of polyester polyol B-1,20 parts of diglycol monotertiary 2-ethylhexyl ether (below be abbreviated as EHDG) and 0.5 part of silane coupling agent (γ-glycidoxypropyltrime,hoxysilane (SHIN-ETSU HANTOTAI's シ リ コ one Application (strain) system)) reaction vessel of packing into, under stream of nitrogen gas, heated 30～60 minutes down at 50 ℃～70 ℃ while stirring, dissolve.

Then, add 0.25 part of ethylene glycol bis dehydration trimellitate, 0.05 part of phosphoric acid, stirred 40 minutes down, dissolve at 100 ℃～120 ℃.

Subsequently, about 80 ℃ down heating mix the polyisocyanate compounds 1 (Trimerization of Isophorone Diisocyanate isocyanic ester: 12 parts, the biuret of HDI: 28 parts) of preparation in 40 parts of synthesis examples 8, make non-solvent adhesive composition of the present invention.With the aftermentioned method this non-solvent adhesive composition is estimated.

In addition, with polyester polyol and ethylene glycol bis dehydration trimellitate mixture heating up to 70 ℃, after it adds the polyisocyanate compounds that is heated to 70 ℃ in advance, measure viscosity under 70 ℃ condition in advance, its viscosity is 3000mPas.(be designated as zero in the viscosity row under 70 ℃ of table 1.And surpass being designated as of 3000mPas *.)

(embodiment 1-2～1-7)

With the ratio shown in the table 1 (weight ratio), the identical non-solvent adhesive composition that makes with embodiment 1-1 carries out same evaluation.All use 0.5 part of silane coupling agent and 0.05 part of phosphoric acid among these external whole embodiment.

(comparative example 1-1～1-12)

With the ratio shown in the table 1 (weight ratio), the identical non-solvent adhesive composition that makes with embodiment 1-1 carries out same evaluation.All use 0.5 part of silane coupling agent and 0.05 part of phosphoric acid in these external whole comparative examples.

In addition, comparative example 1-10 and comparative example 1-11 use デ グ サ ジ ヤ パ Application (strain) system VESTANATT1890/100 (trade(brand)name, Trimerization of Isophorone Diisocyanate isocyanic ester) respectively separately and firmly change バ イ エ Le ウ レ Application (strain) system ス ミ ジ ユ one Le N3200 (trade(brand)name, 1, the biuret of 6-HDI).

(making of sheet layered product)

Make formation A (constructed of aluminium) with following method: the composite membrane of polyethylene terephthalate (the following PET that is designated as sometimes)/aluminium foil (9 microns)/un-stretched polypropylene (the following CPP that is designated as sometimes, 70 microns).

That is, prepared binder composition in each embodiment, the comparative example 80 ℃ of heating mixing down, is coated with solvent-free test coating machine, makes CPP go up glue spread and reach 1.5g/m ²After, coated face and aluminium are carried out lamination, become aluminium/CPP layered product.In addition, identical binder composition is applied on the PET, makes glue spread reach 1.5g/m ²After, the aluminium face of coated face and above-mentioned aluminium/CPP is carried out lamination, obtain PET/ aluminium/CPP structure.

It was preserved 3 in 50 ℃ thermostatic bath, make the sheet layered product.

In addition, the viscosity of non-solvent adhesive composition under 70 surpasses 3000mPas, and then therefore coating difficulty itself can't make the sheet layered product.

Make with following method and to constitute B (transparent evaporation structure): the composite membrane of silica steam plating PET film (following be designated as sometimes silica steam plating PET or (evaporation) PET, 12 microns)/nylon membrane (following be designated as sometimes NY, 15 microns)/CPP (70 microns).

That is, prepared binder composition in each embodiment, the comparative example 80 ℃ of heating mixing down, is coated with solvent-free test coating machine, makes NY go up glue spread and reach 1.5g/m ²After, the evaporation face of coated face and silica steam plating PET is carried out lamination, become silica steam plating PET/NY layered product.In addition, identical binder composition is applied on the CPP, makes glue spread reach 1.5g/m ²After, the NY face of coated face and above-mentioned silica steam plating PET/NY is carried out lamination, obtain silica steam plating PET/NY/CPP structure.

It was preserved 3 in 50 ℃ thermostatic bath, make the sheet layered product.

(binding power test 1 before the distillation)

The sheet layered product that makes in the aforesaid method is cut into 300mm * 15mm, makes coupons.

Using Instron type tensile testing machine, is under the condition of 300mm/min at peeling rate, to each coupons measure between PET/ aluminium, between aluminium/CPP, between silica steam plating PET/NY, and NY/CPP between T type stripping strength (g/15mm, 5 average).

(binding power test 2 before the distillation)

The sheet layered product that makes in the aforesaid method is cut into 300mm * 15mm, make by what the same binder composition was made and constitute between the A or constitute between the B contact in opposite directions between the CPP face of each 2 layered product, sealed under the condition at 190 ℃, 1 second, identical with the situation of binding power test 1 before the above-mentioned distillation, measure heat seal strength between CPP/CPP (g/15mm, average) at 5.

＜anti-distillability 1 〉

(visual valuation)

Use each sheet layered product, under 190 ℃, 1 second heat seal condition, make the sack of 14cm * 18cm size, it is inboard making CPP.To wherein filling 3% aqueous acetic acid, tomato ketchup, salad oil weight ratio blended soup compound 150g (in present specification, being sometimes referred to as 1: 1: 1 soup compound) with 1: 1: 1.

Use rotary type distillation test device, 30r.p.m, 120 ℃, 30 minutes add depress each sack carried out the hot water sterilization after, the state of peeling off between visual observation PET film and aluminium foil, between silica steam plating PET/NY.

* expression is peeled off comprehensively, and zero expression is not peeled off, and △ represents partly to peel off.

(distillation back binding power test 1)

After the visual observation, sack is cut, make the coupons of 300mm * 15mm, with identical before the distillation, to this coupons carry out between PET/ aluminium, T type stripping strength (g/15mm, 5 average) between aluminium/CPP, between silica steam plating PET/NY and between NY/CPP, and the heat seal strength between CPP/CPP (g/15mm, 5 average) is measured.In addition, between visual observation PET film and aluminium foil, silica steam plating PET film and the intermembranous state of peeling off of NY, it is evaluated as * and when (peeling off), each bond strength is not measured comprehensively.

＜distillation after the time estimate

(visual valuation)

Sack is distilled processing, after the visual observation, in 40 ℃ thermostatted, left standstill for 1 week.After 1 week sack taken out, cut, between PET/ aluminium, between aluminium/CPP, silica steam plating PET film and NY is intermembranous and NY/CPP between the state of peeling off carry out visual valuation.

Zero expression is not peeled off, and △ represents partly to peel off, zero-expression partial corrosion, and * expression is peeled off comprehensively.

(distillation after time binding power test)

Behind the visual valuation, make the coupons of wide 15mm, with identical before the distillation, to this coupons carry out between aluminium/CPP and NY/CPP between T type stripping strength (g/15mm, 5 average), and the heat seal strength between CPP/CPP (g/15mm, 5 average) is measured.In addition, between visual observation PET film and aluminium foil, silica steam plating PET film and the intermembranous state of peeling off of NY, it is evaluated as * and when (peeling off), each bond strength is not measured comprehensively.

Table 1

バ イ ロ Application 220: (strain) system trade(brand)name is spun by polyester polyol Japan

バ イ ロ Application GK130: (strain) system trade(brand)name is spun by polyester polyol Japan

Constitute A: aluminium constitutes: PET/ aluminium/CPP

Constitute B: transparent evaporation constitutes: the unit of silica steam plating PET (evaporation face)/NY/CPP addition is part, and empty hurdle is not for adding

Can see that from the result of table 1 its conduct of non-solvent adhesive composition of the present invention is used to make the composite bed press mold tackiness agent of distillation food with wrapping material, excellent performance.

(outward appearance observation)

Use each sheet layered product of the foregoing description 1-1～1-7, comparative example 1-1～1-12, use Toyo Ink to make society's system ア Network ア エ コ one Le or ニ ユ one Off ア イ Application or Off ア イ Application ス one (each trade(brand)name) as printing ink, at surface covered is the sack that creating conditions that 150m/ divides makes 14cm * 18cm size down, and making CPP is the inboard.For embodiment 1-1～1-6, comparative example 1-1～1-12, prepare the sack of above-mentioned formation A, for embodiment 1-7, prepare the sack of above-mentioned formation B.

The sack outward appearance that makes is carried out visual observation, consequently: on printing ink, do not find random mottled deep or lightly, all have good surface appearance.

In addition, use the sheet layered product of embodiment 1-6, except becoming above-mentioned formation B, with the above-mentioned sack that makes equally.Sack outward appearance to the formation B that makes is carried out visual observation, consequently: on printing ink, find random mottled deep or light, appearance poor.

(embodiment 2-1)

With 10 parts of polyester polyol A-1,90 parts of polyester polyol B-1, and 0.5 part of silane coupling agent (γ-glycidoxypropyltrime,hoxysilane (SHIN-ETSU HANTOTAI's シ リ コ one Application (strain) system)) reaction vessel of packing in, under stream of nitrogen gas, heated 30～60 minutes down at 50 ℃～70 ℃ while stirring, dissolve.

Then, add 0.25 part of ethylene glycol bis dehydration trimellitate, stirred 40 minutes down, dissolve at 100 ℃～120 ℃.

Subsequently, about 80 ℃ down heating mix 50 parts of polyisocyanate compounds 1 (Trimerization of Isophorone Diisocyanate isocyanic ester: 15 parts, the biuret of HDI: 35 parts) of preparation in the synthesis examples 8, make non-solvent adhesive composition of the present invention.With the aftermentioned method this non-solvent adhesive composition is estimated.

In addition, with polyester polyol and ethylene glycol bis dehydration trimellitate mixture heating up to 70 ℃, after it adds the polyisocyanate compounds that is heated to 70 ℃ in advance, measure viscosity under 70 ℃ condition in advance, its viscosity is 3000mPas.(be designated as zero in the viscosity row under 70 ℃ of table 2.And surpass being designated as of 3000mPas *.)

(embodiment 2-2～2-6)

With the ratio shown in the table 2 (weight ratio), make the non-solvent adhesive composition in the same manner with embodiment 2-1, carry out same evaluation.All use 0.5 part of silane coupling agent among these external whole embodiment.

(comparative example 2-1～2-12)

With the ratio shown in the table 2 (weight ratio), make the non-solvent adhesive composition in the same manner with embodiment 2-1, carry out same evaluation.All use 0.5 part of silane coupling agent in these external whole comparative examples.

In addition, comparative example 2-10 and comparative example 2-11 use デ グ サ ジ ヤ パ Application (strain) system VESTANATT1890/100 (trade(brand)name, Trimerization of Isophorone Diisocyanate isocyanic ester) respectively separately and firmly change バ イ エ Le ウ レ Application (strain) system ス ミ ジ ユ one Le N3200 (trade(brand)name, 1, the biuret of 6-HDI).

(making of sheet layered product)

Make the composite membrane of polyethylene terephthalate (the following PET that is designated as sometimes)/aluminium foil (9 microns)/un-stretched polypropylene (the following CPP that is designated as sometimes, 70 microns) with following method.

That is, prepared binder composition in each embodiment, the comparative example 80 ℃ of heating mixing down, is coated with solvent-free test coating machine, makes CPP go up glue spread and reach 1.5g/m ²After, coated face and aluminium are carried out lamination, become aluminium/CPP layered product.In addition, identical binder composition is applied on the PET, makes glue spread reach 1.5g/m ²After, the aluminium face of coated face and above-mentioned aluminium/CPP is carried out lamination, obtain PET/ aluminium/CPP structure.

It was preserved 3 in 50 ℃ thermostatic bath, make the sheet layered product.

In addition, the viscosity of non-solvent adhesive composition under 70 surpasses 3000mPas, and then therefore coating difficulty itself can't make the sheet layered product.

(binding power test 2 before the distillation)

The sheet layered product that makes in the aforesaid method is cut into 300mm * 15mm, makes coupons.

Using Instron type tensile testing machine, is under the condition of 300mm/min at peeling rate, measures between PET/ aluminium and the T type stripping strength between aluminium/CPP (g/15mm, average) at 5 to each coupons.

＜anti-distillability 2 〉

(visual valuation 2)

Use each sheet layered product, make the sack of 9cm * 12cm size, it is inboard making CPP.To wherein filling 20g water.

Use rotary type distillation test device, 30r.p.m, 120 ℃, 30 minutes add depress each sack carried out the hot water sterilization after, the state of peeling off between visual observation PET film and aluminium foil.

Zero expression is not peeled off, and △ represents partly to peel off, and * expression is peeled off comprehensively.

(distillation back binding power test 2)

After the visual observation, sack is cut, makes the coupons of 300mm * 15mm, with identical before the distillation, to this coupons carry out between PET/ aluminium and aluminium/CPP between T type stripping strength (g/15mm, 5 average) measure.

Table 2

		Tg(℃)	Mn	Embodiment						Comparative example
																						2-1	2-2	2-3	2-4	2-5	2-6	2-1	2-2	2-3	2-4	2-5	2-6	2-7	2-8	2-9	2-10	2-11	2-12
				Polyester polyol (A)	A-1	27	800	10	20	40	20	20	20					20	20	20	20																			20	20	20	20
A-2	16	600																													80
					A-3	32	390										20
バイロン220	53	2800																									20
					バイロンGK130	13	6800									20
Polyester polyol (B)	B-1	-50	1000																			90	80	60		80	80	80	100	80	80				80	80	80	80					80
				B-2	-50	1000				80
	B-3	-28	6000																														80
				B-4	-26	450													80
	Polyisocyanate compounds 1	The mixture of the biuret (E) of the isocyanuric acid ester of 30 parts of IPDI (D) and 70 parts of HDI																				50	50	50	50	40	60
Trifunctional isocyanates compound (D)					The isocyanuric acid ester of IPDI									15	15	7.5	15	15	3	15	7.5																		30	50	0		15
	Trifunctional isocyanates compound (E)	The biuret of HDI																										35	35	17.5	35	35	7	15	17.5	70	0	50				35
Multi-anhydride (G)					Ethylene glycol bis shrink trimellitate			0.25	0.25	0.25	0.25	0.25	0.25	0.25	0.25	0.25	0.25	0.25	0.25	0.25	0.25																		0.25	0.25	0.25		0.0
	Isocyanate group/hydroxyl																					1.0	1.0	1.0	1.0	0.8	1.2	1.2	1.1	1.1	1.0	1.0	1.0	1.0	0.5	2.0	1.0	1.1				1.0
Viscosity under 70					3000mPa.s below be zero			○	○	○	○	○	○	×	○	×	○	×	×	○	○																		×	×	○		○
	Stripping strength before the distillation	PET/ aluminium																				310	560	330	520	370	300	-	180	-	240	-	-	200	180	-	-	230				330
Aluminium/CPP					1310	1520	1480	1480	1200	1350	-	300	-	480	-	-	300	450	-	-	620																		1100
			Distillation back stripping strength	PET/ aluminium																		280	310	290	300	310	310	-	80	-	180	-	-	150	160	-	-	200		200
Aluminium/CPP							910	1240	1280	1200	800	1160	-	280	-	400	-	-	280	350	-																		-		520	560
				Distillation back visual valuation 2																		○	○	○	○	○	○	-	△	-	△	-	-	△	△	-	-	△		△

バ イ ロ Application 220: (strain) system trade(brand)name is spun by polyester polyol Japan

バ イ ロ Application GK130: (strain) system trade(brand)name is spun by polyester polyol Japan

The unit of addition is part, and empty hurdle is not for adding

Not test of "-" expression

Can see that from the result of table 2 non-solvent adhesive composition of the present invention is as being used to make the composite bed press mold tackiness agent of distillation food with wrapping material, excellent performance.

(embodiment 3-1)

With 10 parts of polyester polyol A-1,90 parts of polyester polyol B-1, and 0.5 part of silane coupling agent (γ-glycidoxypropyltrime,hoxysilane (SHIN-ETSU HANTOTAI's シ リ コ one Application (strain) system)) reaction vessel of packing in, under stream of nitrogen gas, heated 30～60 minutes down at 50 ℃～70 ℃ while stirring, dissolve.

Then, add 0.25 part of ethylene glycol bis dehydration trimellitate, stirred 40 minutes down, dissolve at 100 ℃～120 ℃.

Subsequently, about 80 ℃ down heating mix 50 parts of polyisocyanate compounds 2 (Trimerization of Isophorone Diisocyanate isocyanic ester: 25 parts, the biuret of HDI: 15 parts, isophorone diisocyanate: 10 parts) of preparation in the synthesis examples 10, make non-solvent adhesive composition of the present invention.With the aftermentioned method this non-solvent adhesive composition is estimated.

In addition, with polyester polyol and ethylene glycol bis dehydration trimellitate mixture heating up to 70 ℃, after it adds the polyisocyanate compounds that is heated to 70 ℃ in advance, measure viscosity under 70 ℃ condition in advance, its viscosity is 3000mPas.(be designated as zero in the viscosity row under 70 ℃ of table 3.And surpass being designated as of 3000mPas *.)

(embodiment 3-2～3-6)

With the ratio shown in the table 3 (weight ratio), make the non-solvent adhesive composition in the same manner with embodiment 3-1, carry out same evaluation.All use 0.5 part of silane coupling agent among these external whole embodiment.

(comparative example 3-1～3-12)

With the ratio shown in the table 3 (weight ratio), make the non-solvent adhesive composition in the same manner with embodiment 3-1, carry out same evaluation.All use 0.5 part of silane coupling agent in these external whole comparative examples.

In addition, comparative example 3-10 uses デ グ サ ジ ヤ パ Application (strain) system VESTANATT1890/100 (trade(brand)name, Trimerization of Isophorone Diisocyanate isocyanic ester).

(making of sheet layered product)

Make the composite membrane of polyethylene terephthalate (the following PET that is designated as sometimes)/aluminium foil (9 microns)/un-stretched polypropylene (the following CPP that is designated as sometimes, 70 microns) with following method.

That is, prepared binder composition in each embodiment, the comparative example 80 ℃ of heating mixing down, is coated with solvent-free test coating machine, makes PET go up glue spread and reach 1.5g/m ²After, coated face and aluminium are carried out lamination, make the layered product of PET/ aluminium.In addition, identical binder composition is applied on the aluminium face of this PET/ aluminium, makes glue spread reach 1.5g/m ²After, coated face and CPP are carried out lamination, obtain PET/ aluminium/CPP structure.

It was preserved 3 in 50 ℃ thermostatic bath, make the sheet layered product.

In addition, the viscosity of non-solvent adhesive composition under 70 surpasses 3000mPas, and then therefore coating difficulty itself can't make the sheet layered product.

To each sheet layered product of making as mentioned above, carry out above-mentioned (distillation before binding power test 2) and＜anti-distillability 2 i.e. (visual valuation 2) and (binding power test 2 after the distillation).

Table 3

		Tg (℃)	Mn	Embodiment						Comparative example
																						3-1	3-2	3-3	3-4	3-5	3-6	3-1	3-2	3-3	3-4	3-5	3-6	3-7	3-8	3-9	3-10	3-11	3-12
				Polyester polyol (A)	A-1	27	800	10	20	30	20	20	20					20	20	20	20																			20	20	20	20
A-2	16	600																													80
					A-3	32	390										20
バイロン220	53	2800																									20
					バイロンGK130	13	6800									20
Polyester polyol (B)	B-1	-50	1000																			90	80	70		80	80	80	100	80	80				80	80	80	80					80
				B-2	-50	1000				80
	B-3	-28	6000																														80
				B-4	-26	450													80
	Polyisocyanate compounds 2	The biuret (E) of the isocyanuric acid ester of 50 parts of IPDI (D), 30 parts of HMDI and the mixture of 20 parts of IPDI (F)																				50	50	50	50	40	60
Trifunctional isocyanates compound (D)					The isocyanuric acid ester of IPDI									25	25	12.5	25	20	3.75	25	12.5																		50	60			25
	Trifunctional isocyanates compound (E)	The biuret of HDI																										15	15	7.5	15	12	225	15	75	30		50				15
Isocyanate compound (F)					IPDI									10	10	5.0	10	8	1.5	10	5.0																		20				10
	Multi-anhydride (G)	Ethylene glycol bis shrink trimellitate																				0.25	0.25	0.25	0.25	0.25	0.25	0.25	0.25	0.25	0.25	0.25	0.25	0.25	0.25	0.25	0.25	0.25				0.0
Isocyanate group/hydroxyl					0.9	1.0	1.1	1.0	0.8	1.2	1.2	0.9	1.1	0.8	1.1	1.1	0.8	0.5	2.0	1.0	1.1																		1.0
				Viscosity under 70																		3000mPa.s below be zero			○	○	○	○	○	○	×	○	×	○	×	×	○	○		×	×	○	○
Stripping strength before the distillation	PET/ aluminium				310	590	500	510	390	330	-	190	-	220	-	-	180	150	-	-	230																		350
				Aluminium/CPP																		1310	1450	1480	1400	1280	1400	-	310	-	500	-	-	310	430	-	-	620		1100
	Distillation back stripping strength	PET/ aluminium					280	320	310	300	330	330	-	80	-	100	-	-	170	150	-																		-		200	250
Aluminium/CPP					910	1250																1280	1250	1000	1220	-	290	-	350	-	-	250	330	-	-	520	580
			Distillation back visual valuation 2				○	○	○	○	○	○	-	△	-	△	-	-	△	△	-																	-	△	△

バ イ ロ Application 220: (strain) system trade(brand)name is spun by polyester polyol Japan

バ イ ロ Application GK130: (strain) system trade(brand)name is spun by polyester polyol Japan

The unit of addition is part, and empty hurdle is not for adding

Not test of "-" expression

Can see that from the result of table 3 its conduct of non-solvent adhesive composition of the present invention is used to make the composite bed press mold tackiness agent of distillation food with wrapping material, excellent performance.

More than describe the present invention by example, as long as we do not particularly point out, any thin portion in the invention is not restricted to illustrate under the situation of the spirit and scope of the present invention shown in the appended claim scope, can explain widely.

The application with on April 26th, 2002 spy in Japanese publication be willing to 2002-127087, on June 28th, 2002 spy in Japanese publication be willing to 2002-190568 and on September 27th, 2002 spy in Japanese publication be willing to that 2002-282279 is a right of priority, the present invention invents with reference to all these, and their content is introduced the part as specification sheets record of the present invention.

Claims (16)

1. non-solvent adhesive composition is characterized in that it contains:

The second-order transition temperature of (1) 5～70 weight % is that 10～40 ℃, number-average molecular weight are that the second-order transition temperature of 500～2000 polyester polyol (A), 20～95 weight % is 500～2000 polyester polyol (B) and the monofunctional alcohol (C) of 0～30 weight % for-70～0 ℃, number-average molecular weight, wherein polyester polyol (A) and (B) and monofunctional alcohol (C) add up to 100 weight %;

(2) the trifunctional isocyanates compound (D) that (i) is formed by alicyclic diisocyanate compound or aromatic diisocyanate compounds reaches the trifunctional isocyanates compound (E) by the aliphatic diisocyanate compound formation, the number of the hydroxyl that adds up in the isocyanate group that wherein above-mentioned trifunctional isocyanates compound (D) adds up in reaching (E) and above-mentioned polyester polyol (A), (B) and the monofunctional alcohol (C) is counted 0.7/1.0～1.5/1.0 than with isocyanate group/hydroxyl, or

(ii) the trifunctional isocyanates compound (D) that forms by alicyclic diisocyanate compound or aromatic diisocyanate compounds, by the trifunctional isocyanates compound (E) of aliphatic diisocyanate compound formation, and diisocyanate cpd (F), the number of the hydroxyl of total is counted 0.7/1.0～1.5/1.0 than with isocyanate group/hydroxyl in the isocyanate group that adds up in wherein above-mentioned trifunctional isocyanates compound (D), (E) and the diisocyanate cpd (F) and above-mentioned polyester polyol (A), (B) and the monofunctional alcohol (C); And

(3) multi-anhydride (G).

2. according to the non-solvent adhesive composition of claim 1 record, it is characterized in that it contains the oxygen acid or derivatives thereof (H) of phosphorus.

3. according to the non-solvent adhesive composition of claim 1 record, it is characterized in that polyester polyol (B) is the polyester polyol (B2) that does not contain the polyester polyol (B1) of ehter bond and/or contain ehter bond.

4. non-solvent adhesive composition is characterized in that it is combined with:

(1) second-order transition temperature that contains 5～70 weight % is that 10～40 ℃, number-average molecular weight are that the second-order transition temperature of 500～2000 polyester polyol (A), 20～95 weight % is 500～2000 polyester polyol (B) and the monofunctional alcohol (C) of 0～30 weight % for-70～0 ℃, number-average molecular weight, wherein polyester polyol (A) and (B) and monofunctional alcohol (C) add up to 100 weight %, and the 1st composition of multi-anhydride (G) and

(2) (i) contain the trifunctional isocyanates compound (D) that forms by alicyclic diisocyanate compound or aromatic diisocyanate compounds and by the trifunctional isocyanates compound (E) of aliphatic diisocyanate compound formation or (ii) contain the trifunctional isocyanates compound (D) that forms by alicyclic diisocyanate compound or aromatic diisocyanate compounds, trifunctional isocyanates compound (E) by the aliphatic diisocyanate compound formation, and the 2nd composition of diisocyanate cpd (F)

Make above-mentioned trifunctional isocyanates compound (D) reach (E) middle isocyanate group and the above-mentioned polyester polyol (A) that adds up to, (B) and the number of the hydroxyl that adds up in the monofunctional alcohol (C) than being isocyanate group/hydroxyl=0.7/1.0～1.5/1.0 or above-mentioned trifunctional isocyanates compound (D), (E) and the isocyanate group and the above-mentioned polyester polyol (A) that add up in the diisocyanate cpd (F), (B) and the number of the hydroxyl that adds up in the monofunctional alcohol (C) than counting 0.7/1.0～1.5/1.0 with isocyanate group/hydroxyl.

5. according to the non-solvent adhesive composition of claim 4 record, it is characterized in that the 1st composition contains the oxygen acid or derivatives thereof (H) of phosphorus.

6. according to the non-solvent adhesive composition of claim 4 record, it is characterized in that polyester polyol (B) is the polyester polyol (B2) that does not contain the polyester polyol (B1) of ehter bond and/or contain ehter bond.

7. according to the non-solvent adhesive composition of claim 2 or 5 records, it is characterized in that for the polyester polyol (A), (B) and the monofunctional alcohol (C) that add up to 100 weight parts, the oxygen acid or derivatives thereof (H) of phosphorus is 0.01～5 weight part.

8. according to the non-solvent adhesive composition of any one record in the claim 1～6, it is characterized in that the trifunctional isocyanates compound (D1) of trifunctional isocyanates compound (D) for alicyclic diisocyanate compound or the esterification of aromatic diisocyanate compounds cyamelide are formed.

9. according to the non-solvent adhesive composition of any one record in the claim 1～6, it is characterized in that trifunctional isocyanates compound (E) is for the biuretized trifunctional isocyanates compound (E1) that forms of aliphatic diisocyanate compound.

10. according to the non-solvent adhesive composition of any one record in the claim 1～6, it is characterized in that diisocyanate cpd (F) is alicyclic diisocyanate compound (F1).

11. the non-solvent adhesive composition according to any one record in the claim 1～6 is characterized in that, multi-anhydride (G) is the trimellitate acid anhydride shown in following formula (1) or (2).

12. a sheet material that has binder layer is characterized in that, its by under heating with claim 1～6 in the non-solvent adhesive composition of any one record be applied to flat substrates and form on the one side at least.

13. a manufacture method that has the sheet material of binder layer is characterized in that, it is included in heating and down the non-solvent adhesive composition of any one record in the claim 1～6 is applied to the flat substrates step on the one side at least.

14. a sheet layered product is characterized in that, it forms by the binder layer of the sheet material that has binder layer of claim 12 record and other flat substrates are carried out lamination.

15. a sheet laminated body manufacturing method is characterized in that, its binder layer and other flat substrates that is included in the sheet material of under the heating claim 12 being put down in writing that has binder layer carries out laminated step.

16. sheet laminated body manufacturing method, it is characterized in that, its be included in heating down the non-solvent adhesive composition of any one record in the claim 1～6 is applied to flat substrates at least one side go up and form binder layer, under heating, make other flat substrates and this binder layer carry out laminated each step then.