Saturated polyester copolymer as well as preparation method and application thereof

Abstract

The invention discloses a saturated polyester copolymer as well as a preparation method and application thereof, and belongs to the technical field of polymer materials. The saturated polyester copolymer provided by the invention is prepared from the following raw materials: a compound a, a compound b, a compound c, polyol and a catalyst, the polybasic acid and / or polybasic acid anhydride are / is included; structural components with carbon atoms shared by carbon rings, namely the compound a and the compound b, are introduced into the saturated polyester copolymer, more ordered distribution of space groups in chain segments can be achieved, the improvement effect on the adhesive force of various base materials is remarkable, the contractility of a coating is obviously reduced, in addition, the heat resistance of the coating is improved, and in addition, the heat resistance of the coating is improved. Meanwhile, a hydroquinone or hydroquinone-like structure is synchronously introduced, the heat resistance of a polyester chain segment is effectively improved, and when the saturated polyester copolymer is used for preparing printing ink for in-mold injection molding decoration, the performance requirement of an in-mold injection molding process can be effectively met.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials, and in particular relates to a saturated polyester copolymer and a preparation method and application thereof. Background Art

[0002] In-Mold Decoration (IMD) technology is a new technology that replaces the painting and electroplating of plastic products. It places the sheet in the mold cavity for injection molding. The injection resin is combined with the printed ink layer on the back of the sheet. The ink layer is placed between the sheet and the injection-molded resin. The resin and the sheet are bonded together and solidified. The surface of the IMD product is a hardened transparent film, the middle is an ink pattern layer, and the back is an injection layer. IMD technology increases the design freedom. The pattern color is in the plastic interlayer, which improves the wear resistance and maintains the color for a long time.

[0003] IMD ink, as a key material in IMD process technology, has high performance requirements. After curing, the ink needs to have excellent elongation and high temperature resistance. The resin used in IMD ink needs to have good temperature resistance, tensile flexibility, adhesion, surface hardness, impact resistance and low shrinkage.

[0004] The shapes and sizes of plastic parts in the IMD process vary, and there are thermal shrinkage and stress changes before and after molding. IMD inks currently have unstable adhesion on optical coatings and poor versatility. Their high temperature resistance and toughness are not adaptable enough to meet the performance indicators of the IMD process. Conventional linear or hyperbranched polyesters have not yet met the requirements for resins used in IMD inks. Summary of the invention

[0005] In order to overcome at least one of the problems existing in the above-mentioned prior art, one of the objects of the present invention is to provide a saturated polyester copolymer, which has good properties such as temperature resistance, tensile flexibility, adhesion, surface hardness, impact resistance and low shrinkage, and is particularly suitable for preparing inks for in-mold decoration (IMD).

[0006] A second object of the present invention is to provide a method for preparing the saturated polyester copolymer.

[0007] A third object of the present invention is to provide an application of the saturated polyester copolymer.

[0008] In order to achieve the above object, the technical solution adopted by the present invention is:

[0009] The first aspect of the present invention provides a saturated polyester copolymer, wherein the raw materials for preparing the saturated polyester copolymer include: compound a, compound b, compound c, polyol, catalyst; and also include polyacid and / or polyacid anhydride;

[0010] The chemical formula of the compound a is shown in Formula 1:

[0011]

[0012] The chemical formula of the compound b is shown in Formula 2:

[0013]

[0014] The chemical formula of the compound c is shown in Formula 3:

[0015]

[0016] In Formula 1, each R1 is independently selected from a hydroxyl group, a carboxyl group or an amino group, and at least one R1 is a hydroxyl group; n1≥1 and n1 is an integer;

[0017] In Formula 2, each R2 is independently selected from a hydroxyl group, a carboxyl group or an amino group, and at least one R2 is a hydroxyl group; each X is independently selected from a C1 to C10 alkyl group; 1≤n2≤5 and n2 is an integer;

[0018] In Formula 3, each R3 is independently selected from a hydroxyl group, a carboxyl group or an amino group, and at least one R3 is a hydroxyl group; n3≥2 and n3 is an integer.

[0019] Among the existing polyester materials, some directly use monomers containing only alicyclic groups and monomers containing only benzene ring groups as synthetic raw materials, resulting in the heterogeneity of the synthesized polyester chain segment groups; others use conventional aliphatic or single benzene ring aromatic polyacids or alcohols to synthesize polyesters, which have poor flexibility and heat resistance and are difficult to adapt to the process characteristics of IMD inks. Compared with the existing polyester materials, the present invention introduces structural components of carbon rings sharing carbon atoms, namely compounds a and b, into polyester copolymers, which can achieve a more orderly distribution of spatial groups in the chain segments, not only significantly improving the adhesion of various substrates, but also significantly reducing the shrinkage of the coating, effectively meeting the performance requirements of the in-mold injection molding process, and combining the alicyclic structure compound c and polyacids (anhydrides) and polyols, the obtained saturated polyester copolymer has good heat resistance, tensile flexibility, adhesion, surface hardness, impact resistance and low shrinkage, etc., and is particularly suitable for preparing inks for in-mold decoration (IMD).

[0020] Preferably, in Formula 1, each R1 is independently selected from hydroxyl or amino, and at least one R1 is a hydroxyl group; further preferably, in Formula 1, each R1 is identically selected from hydroxyl or amino, and compound a is a mixture of different compounds of Formula 1, and at least one R1 of the compound of Formula 1 in compound a is selected from a hydroxyl group; further preferably, in Formula 1, each R1 is identically selected from a hydroxyl group.

[0021] Preferably, when compound a is a mixture of different compounds of formula 1, and part of R1 is selected from hydroxyl groups and the other part of R1 is selected from amino groups, the molar content of hydroxyl groups in compound a is greater than the molar content of amino groups.

[0022] Preferably, in Formula 1, n1 is 1 to 10 and is an integer; further preferably, in Formula 1, n1 is 1 to 5 and is an integer; for example, n1 is 1, 2, 3, 4 or 5; further preferably, in Formula 1, n1 is 1.

[0023] In some specific embodiments of the present invention, compound a is selected from 2-methylspiro[3.5]nonane-2,7-diol.

[0024] Preferably, the mass proportion of compound a in the total amount of raw materials for preparing the polyester copolymer is 0.5-40wt%; further preferably, the mass proportion of compound a in the total amount of raw materials for preparing the polyester copolymer is 0.8-30wt%; even more preferably, the mass proportion of compound a in the total amount of raw materials for preparing the polyester copolymer is 1-20wt%; non-limiting specific examples are 3wt%, 5wt%, 8wt%, 10wt%, 13wt%, 15wt% or 18wt%.

[0025] Preferably, in Formula 2, each R2 is independently selected from hydroxyl or amino, and at least one R2 is a hydroxyl group; further preferably, in Formula 2, each R2 is identically selected from hydroxyl or amino, and compound b is a mixture of different compounds of Formula 2, and at least one R2 of the compound of Formula 2 in compound b is selected from a hydroxyl group; further preferably, in Formula 2, each R2 is identically selected from a hydroxyl group.

[0026] Preferably, when compound b is a mixture of different compounds of formula 2, and part of R2 is selected from hydroxyl groups and the other part of R2 is selected from amino groups, the molar content of hydroxyl groups in compound b is greater than the molar content of amino groups.

[0027] Preferably, in Formula 2, each X is independently selected from C1 to C8 alkyl; further preferably, in Formula 2, each X is independently selected from C1 to C5 alkyl; further preferably, in Formula 2, each X is independently selected from methyl or ethyl.

[0028] Preferably, in Formula 2, 1≤n2≤3 and n2 is an integer; for example, n2 is 1, 2 or 3; further preferably, in Formula 2, n2 is 1.

[0029] In some specific embodiments of the present invention, compound b is selected from 4,8-tricyclo[5.2.1.02,7]decanedimethanol.

[0030] Preferably, the mass proportion of compound b in the total amount of raw materials for preparing the polyester copolymer is 0.5-60wt%; further preferably, the mass proportion of compound b in the total amount of raw materials for preparing the polyester copolymer is 1-50wt%; even more preferably, the mass proportion of compound b in the total amount of raw materials for preparing the polyester copolymer is 5-40wt%; non-limiting specific examples are 10wt%, 15wt%, 20wt%, 25wt%, 30wt% or 35wt%.

[0031] Preferably, in Formula 3, each R3 is independently selected from hydroxyl or amino, and at least one R3 is hydroxyl; further preferably, in Formula 3, each R3 is identically selected from hydroxyl or amino, and compound c is a mixture of different compounds of Formula 3, and at least one R3 of compound c of Formula 3 is selected from hydroxyl; further preferably, in Formula 3, each R3 is identically selected from hydroxyl.

[0032] Preferably, when compound c is a mixture of different compounds of formula 3, and part of R3 is selected from hydroxyl groups and the other part of R3 is selected from amino groups, the molar content of hydroxyl groups in compound c is greater than the molar content of amino groups.

[0033] Preferably, in Formula 3, n3 is 2 to 10 and is an integer; further preferably, in Formula 3, n3 is 2 to 5; for example, n3 is 2, 3, 4 or 5; further preferably, in Formula 3, n3 is 2.

[0034] In some specific embodiments of the present invention, compound c is selected from 4,4'-dihydroxybicyclohexane.

[0035] Preferably, the mass proportion of compound c in the total amount of raw materials for preparing the polyester copolymer is 0.5-40wt%; further preferably, the mass proportion of compound c in the total amount of raw materials for preparing the polyester copolymer is 0.8-30wt%; even more preferably, the mass proportion of compound c in the total amount of raw materials for preparing the polyester copolymer is 1-20wt%; non-limiting specific examples are 3wt%, 5wt%, 8wt%, 10wt%, 13wt%, 15wt% or 18wt%.

[0036] Preferably, the mass ratio of the compound b is greater than the mass ratio of the compound a; further preferably, the mass ratio of the compound b to the compound a is 1:(0.1-0.9).

[0037] Preferably, the mass ratio of the compound b is greater than the mass ratio of the compound c; further preferably, the mass ratio of the compound b to the compound c is 1:(0.1-0.9).

[0038] Preferably, the polyol includes a first polyol, or a combination of a first polyol and a second polyol; the first polyol includes a polyol containing a C6-C20 aromatic group and / or an ether group; the second polyol includes a C2-C20 fatty polyol, a C5-C20 alicyclic polyacid or a combination thereof.

[0039] Preferably, the first polyol comprises a polyol containing a C6-C20 aromatic group and an ether group; further preferably, the first polyol comprises a polyol containing a phenyl group and an ether group; even more preferably, the first polyol comprises dihydroxyethyl hydroquinone ether, hydroxyethylated bisphenol A or a combination thereof; more preferably, the first polyol is selected from dihydroxyethyl hydroquinone ether, or selected from dihydroxyethyl hydroquinone ether and hydroxyethylated bisphenol A.

[0040] Furthermore, in addition to introducing structural components of carbon ring shared carbon atoms, a first polyol having a specific hydroquinone or hydroquinone-like structure is also used. By introducing the hydroquinone or hydroquinone-like structure, the heat resistance of the polyester chain segment is effectively improved, which is beneficial to inhibit the thermal degradation of the ink layer during the in-mold injection molding process and maintain the comprehensive performance of the ink layer in the IMD process stable.

[0041] Preferably, the second polyol includes C2-C15 fatty polyol, C5-C15 alicyclic polyacid or a combination thereof; further preferably, the second polyol includes at least one of neopentyl glycol, ethylene glycol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 1,4-cyclohexanedimethanol, hexadecanediol, trimethylolpropane or trimethylolethane; further preferably, the second polyol includes at least one of neopentyl glycol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol or trimethylolpropane; more preferably, the second polyol includes neopentyl glycol, 2-methyl-1,3-propanediol or a combination thereof.

[0042] Preferably, the polyacid includes at least one of C6-C20 aromatic polyacids, C2-C20 fatty polyacids or C5-C20 alicyclic polyacids; further preferably, the polyacid includes at least one of C6-C15 aromatic polyacids, C5-C15 fatty polyacids or C7-C15 alicyclic polyacids.

[0043] Preferably, the polyacid includes at least one of adipic acid, suberic acid, sebacic acid, dodecanedioic acid, cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid or trimellitic acid; further preferably, the polyacid includes at least one of adipic acid, suberic acid, sebacic acid, terephthalic acid, isophthalic acid or trimellitic acid; even more preferably, the polyacid includes at least one of adipic acid, terephthalic acid, isophthalic acid or trimellitic acid.

[0044] Preferably, the polyacid anhydride includes at least one of C6-C20 aromatic polyacid anhydrides, C2-C20 fatty polyacid anhydrides or C5-C20 alicyclic polyacid anhydrides; further preferably, the polyacid anhydride includes at least one of C6-C15 aromatic polyacid anhydrides, C5-C15 fatty polyacid anhydrides or C7-C15 alicyclic polyacid anhydrides.

[0045] Preferably, the polyacid anhydride includes at least one of adipic anhydride, suberic anhydride, sebacic anhydride, dodecanedioic anhydride, cyclohexanedicarboxylic anhydride or trimellitic anhydride; further preferably, the polyacid anhydride includes at least one of adipic anhydride, suberic anhydride, sebacic anhydride, dodecanedioic anhydride or trimellitic anhydride; even more preferably, the polyacid anhydride includes adipic anhydride, trimellitic anhydride or a combination thereof.

[0046] Preferably, the ratio of the total molar amount of compound a, compound b, compound c and polyol to the total molar amount of the polyacid and / or polyacid anhydride is (0.9-3.5):1; further preferably, the ratio of the total molar amount of compound a, compound b, compound c and polyol to the total molar amount of the polyacid and / or polyacid anhydride is (0.9-3):1; further preferably, the ratio of the total molar amount of compound a, compound b, compound c and polyol to the total molar amount of the polyacid and / or polyacid anhydride is (0.9-2.5):1; non-limiting specific examples are 1:1, 1.5:1 or 2:1.

[0047] Preferably, the catalyst comprises at least one of a tin catalyst, an antimony catalyst or a titanium catalyst; further preferably, the catalyst comprises a tin catalyst, a titanium catalyst or a combination thereof.

[0048] Preferably, the number average molecular weight of the saturated polyester copolymer is 5 to 50 kDa; more preferably, the number average molecular weight of the saturated polyester copolymer is 7 to 45 kDa; more preferably, the number average molecular weight of the saturated polyester copolymer is 9 to 40 kDa; more preferably, the number average molecular weight of the saturated polyester copolymer is 10 to 35 kDa. Non-limiting specific examples include 12 kDa, 15 kDa, 18 kDa, 20 kDa, 25 kDa or 30 kDa.

[0049] Preferably, the glass transition temperature of the saturated polyester copolymer is -20 to 70°C; more preferably, the glass transition temperature of the saturated polyester copolymer is -10 to 60°C; more preferably, the glass transition temperature of the saturated polyester copolymer is 0 to 55°C; more preferably, the glass transition temperature of the saturated polyester copolymer is 10 to 50°C. Non-limiting specific examples include 15°C, 20°C, 25°C, 30°C, 35°C, 40°C or 45°C.

[0050] Preferably, the acid value of the saturated polyester copolymer is 1 to 20 mgKOH / g; more preferably, the acid value of the saturated polyester copolymer is 2 to 15 mgKOH / g; more preferably, the acid value of the saturated polyester copolymer is 3 to 10 mgKOH / g. Non-limiting specific examples include 3.5 mgKOH / g, 4 mgKOH / g, 5 mgKOH / g, 6 mgKOH / g, 7 mgKOH / g, 8 mgKOH / g or 9 mgKOH / g.

[0051] Preferably, the hydroxyl value of the saturated polyester copolymer is 10-50 mgKOH / g; more preferably, the hydroxyl value of the saturated polyester copolymer is 3-45 mgKOH / g; more preferably, the hydroxyl value of the saturated polyester copolymer is 5-40 mgKOH / g. Non-limiting specific examples include 15 mgKOH / g, 18 mgKOH / g, 20 mgKOH / g, 22 mgKOH / g, 25 mgKOH / g, 30 mgKOH / g or 35 mgKOH / g.

[0052] The second aspect of the present invention provides a method for preparing the saturated polyester copolymer according to the first aspect of the present invention, comprising the following steps:

[0053] S1, mixing compound a, compound c, polyol, part of compound b, polyacid and / or polyacid anhydride, and catalyst, and performing a first polymerization reaction in a protective gas atmosphere to obtain a first polymer;

[0054] S2, adding the remaining amount of compound b, polyacid and / or polyacid anhydride to the first polymer, and performing a second polymerization reaction in a protective gas atmosphere to obtain a second polymer;

[0055] S3, adding the remaining amount of catalyst to the second polymer, and performing vacuum polycondensation reaction to obtain the saturated polyester copolymer.

[0056] Preferably, the temperature of the first polymerization reaction is 200-260°C; more preferably, the temperature of the first polymerization reaction is 220-240°C.

[0057] Preferably, the temperature of the second polymerization reaction is 200-260°C; more preferably, the temperature of the second polymerization reaction is 220-240°C.

[0058] Preferably, there is a temperature rising process between the second polymerization reaction and the vacuum polycondensation reaction.

[0059] Preferably, the temperature of the vacuum polycondensation reaction is 220-280°C; further preferably, the temperature of the vacuum polycondensation reaction is 230-260°C.

[0060] Preferably, the reaction endpoint of the first polymerization reaction is that the acid value of the first polymer is ≤20 mgKOH / g; further preferably, the reaction endpoint of the first polymerization reaction is that the acid value of the first polymer is ≤18 mgKOH / g; further preferably, the reaction endpoint of the first polymerization reaction is that the acid value of the first polymer is ≤15 mgKOH / g.

[0061] Preferably, the reaction endpoint of the second polymerization reaction is that the acid value of the second polymer is ≤35 mgKOH / g; further preferably, the reaction endpoint of the second polymerization reaction is that the acid value of the second polymer is ≤30 mgKOH / g; further preferably, the reaction endpoint of the second polymerization reaction is that the acid value of the second polymer is ≤28 mgKOH / g.

[0062] Preferably, the vacuum degree of the vacuum polycondensation reaction is ≤600Pa.

[0063] The third aspect of the present invention provides an ink for in-mold decoration (IMD), comprising the saturated polyester copolymer described in the first aspect of the present invention.

[0064] Preferably, the in-mold molding decorative ink further comprises a curing agent, an amino resin or a combination thereof.

[0065] Preferably, the curing agent is selected from isocyanate compounds; further preferably, the isocyanate compound includes at least one of diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, di(isocyanatomethyl)cyclohexane, cyclohexane diisocyanate, dicyclohexylmethane diisocyanate or corresponding blocked isocyanate compounds.

[0066] Preferably, the amino resin comprises at least one of methyl etherified amino resin, ethyl etherified amino resin, propyl etherified amino resin or butyl etherified amino resin; further preferably, the amino resin comprises methyl etherified amino resin, butyl etherified amino resin or a combination thereof.

[0067] Preferably, the methyl etherified amino resin includes partially methyl etherified amino resin, fully methyl etherified amino resin or a combination thereof.

[0068] The saturated polyester copolymer of the present invention can be used as the main adhesive for preparing ink for in-mold decoration (IMD), can form a coating in the form of a single component, and can also undergo a cross-linking reaction with components such as isocyanate compounds and / or amino resins to obtain a cured coating, which can meet the performance requirements of the ink for IMD, such as excellent coating temperature resistance, tensile flexibility, adhesion, surface hardness, impact resistance, and low shrinkage.

[0069] The beneficial effects of the present invention are as follows: the present invention introduces structural components of carbon rings sharing carbon atoms, namely compound a and compound b, into the saturated polyester copolymer, which can achieve a more orderly distribution of spatial groups in the chain segment, which not only significantly improves the adhesion to various substrates, but also significantly reduces the shrinkage of the coating. In addition, in addition to introducing structural components of carbon rings sharing carbon atoms, the present invention also simultaneously introduces hydroquinone or hydroquinone-like structures, which effectively improves the heat resistance of the polyester chain segment. When the saturated polyester copolymer of the present invention is used to prepare in-mold injection molding decorative ink, it can effectively meet the performance requirements of the in-mold injection molding process, can inhibit the thermal degradation of the ink layer in the in-mold injection molding process, and maintain the comprehensive performance of the ink layer in the in-mold injection molding decorative process stable.

[0070] Specifically, compared with the prior art, the present invention has the following advantages:

[0071] 1. The present invention introduces a structural component of a carbon ring sharing a carbon atom through compound a and compound b, which effectively improves the distribution order of the polyester chain segment, and also adopts a first polyol with a specific structure, introduces a hydroquinone or a hydroquinone-like structure, and effectively improves the heat resistance of the polyester chain segment, which is beneficial to inhibit the thermal degradation of the ink layer during the in-mold injection molding process and maintain the comprehensive performance of the ink layer in the IMD process.

[0072] 2. The present invention changes the application mode of existing IMD inks in which the performance requirements of the ink layer are achieved by sharing multiple types of adhesive resins. The saturated polyester copolymer of the present invention, as the main film-forming substance, can form a coating in the form of a single adhesive, and can also be combined with an isocyanate curing agent and / or an amino resin to form a coating. The prepared IMD ink coating can break through the technical bottleneck of the ink layer being difficult to adhere to and easy to fall off the plastic substrate, significantly improve the stable adhesion performance of the coating in the IMD process, and further enhance the comprehensive performance of the coating, such as temperature resistance, tensile flexibility, adhesion, surface hardness, impact resistance and low shrinkage. DETAILED DESCRIPTION

[0073] The content of the present invention is further described in detail below through specific examples. It should also be understood that the following examples are only used to further illustrate the present invention and cannot be construed as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the principles set forth in the present invention all belong to the scope of protection of the present invention. The specific process parameters and the like in the following examples are also only examples within a suitable range, that is, those skilled in the art can make a selection within a suitable range through the description herein, and are not limited to the specific data exemplified below. The raw materials, reagents or devices used in the following examples and comparative examples, unless otherwise specified, can all be obtained from conventional commercial sources, or can be obtained by existing known methods.

[0074] Example 1

[0075] This example provides a saturated polyester copolymer, and the raw materials for preparation are as follows: 2-methylspiro[3.5]nonane-2,7-diol, 4,8-tricyclo[5.2.1.O2,7]decanedimethanol, 4,4'-dihydroxydicyclohexane, 2-methyl-1,3-propanediol, neopentyl glycol, hydroquinone dihydroxyethyl ether, terephthalic acid, isophthalic acid, adipic acid and tin catalyst. The specific amounts are shown in Table 1.

[0076] The preparation method of the saturated polyester copolymer of this example specifically comprises the following steps (the raw materials and amounts used in each step are shown in Table 1):

[0077] (1) In a reaction kettle equipped with a stirrer, a thermometer, a reflux condenser and nitrogen, the raw materials required for the first step reaction are added into the reactor according to the corresponding amounts shown in Table 1, including 2-methylspiro[3.5]nonane-2,7-diol, 4,8-tricyclo[5.2.1.O2,7]decanedimethanol, 4,4'-dihydroxydicyclohexane, 2-methyl-1,3-propanediol, neopentyl glycol, hydroquinone dihydroxyethyl ether, terephthalic acid, isophthalic acid, adipic acid and a tin catalyst. Under a protective atmosphere of nitrogen, the temperature is gradually increased and kept at 220-240° C. for 4-6 hours, until the acid value of the system is reduced to below 20 mgKOH / g.

[0078] (2) Maintaining the reaction conditions of step (1), the raw materials required for the second step reaction, including 4,8-tricyclo[5.2.1.O2,7]decanedimethanol and isophthalic acid, were added in the corresponding amounts shown in Table 1, and the reaction was carried out until the acid value of the system was reduced to below 30 mgKOH / g.

[0079] (3) A tin catalyst was added in an amount shown in Table 1, and vacuum polycondensation was carried out at 230-260° C. (vacuum degree ≤ 600 Pa) to react to a target viscosity to obtain a saturated polyester copolymer CP1.

[0080] Example 2

[0081] This example provides a saturated polyester copolymer, and the raw materials for preparation are as follows: 2-methylspiro[3.5]nonane-2,7-diol, 4,8-tricyclo[5.2.1.O2,7]decanedimethanol, 4,4'-dihydroxydicyclohexane, 2-methyl-1,3-propanediol, neopentyl glycol, hydroxyethylated bisphenol A, terephthalic acid, isophthalic acid, adipic acid and antimony catalyst. The specific amounts are shown in Table 1.

[0082] The preparation method of the saturated polyester copolymer of this example specifically comprises the following steps (the raw materials and amounts used in each step are shown in Table 1):

[0083] (1) In a reaction kettle equipped with a stirrer, a thermometer, a reflux condenser and nitrogen, the raw materials required for the first step reaction are added into the reactor according to the corresponding amounts shown in Table 1, including 2-methylspiro[3.5]nonane-2,7-diol, 4,8-tricyclo[5.2.1.O2,7]decanedimethanol, 4,4'-dihydroxydicyclohexane, 2-methyl-1,3-propanediol, neopentyl glycol, hydroxyethylated bisphenol A, terephthalic acid, isophthalic acid and antimony catalyst. Under a protective atmosphere of nitrogen, the temperature is gradually increased and kept at 220-240° C. for 4-6 hours, until the acid value of the system is reduced to below 18 mgKOH / g.

[0084] (2) Maintaining the reaction conditions of step (1), the raw materials required for the second step reaction, including 4,8-tricyclo[5.2.1.O2,7]decanedimethanol and adipic acid, were added in the corresponding amounts shown in Table 1, and the reaction was carried out until the acid value of the system was reduced to below 28 mgKOH / g.

[0085] (3) Add an antimony catalyst in the amount shown in Table 1, carry out vacuum polycondensation at 230-260° C. (vacuum degree ≤ 600 Pa), and react until the target viscosity is reached to obtain a saturated polyester copolymer CP2.

[0086] Example 3

[0087] This example provides a saturated polyester copolymer, and the raw materials for preparation are as follows: 2-methylspiro[3.5]nonane-2,7-diol, 4,8-tricyclo[5.2.1.O2,7]decanedimethanol, 4,4'-dihydroxydicyclohexane, 2-methyl-1,3-propanediol, neopentyl glycol, hydroquinone dihydroxyethyl ether, terephthalic acid, isophthalic acid, adipic acid, cyclohexanedicarboxylic acid and titanium catalyst. The specific amounts are shown in Table 1.

[0088] The preparation method of the saturated polyester copolymer of this example specifically comprises the following steps (the raw materials and amounts used in each step are shown in Table 1):

[0089] (1) In a reaction kettle equipped with a stirrer, a thermometer, a reflux condenser and nitrogen, the raw materials required for the first step reaction are added into the reactor according to the corresponding amounts shown in Table 1, including 2-methylspiro[3.5]nonane-2,7-diol, 4,8-tricyclo[5.2.1.O2,7]decanedimethanol, 4,4'-dihydroxydicyclohexane, 2-methyl-1,3-propanediol, neopentyl glycol, hydroquinone dihydroxyethyl ether, terephthalic acid, isophthalic acid, adipic acid and a titanium catalyst. Under a protective atmosphere of nitrogen, the temperature is gradually increased and kept at 220-240° C. for 4-6 hours, until the acid value of the system is reduced to below 15 mgKOH / g.

[0090] (2) Maintaining the reaction conditions of step (1), the raw materials required for the second step reaction, including 4,8-tricyclo[5.2.1.O2,7]decanedimethanol and cyclohexanedicarboxylic acid, were added in the corresponding amounts shown in Table 1, and the reaction was carried out until the acid value of the system was reduced to below 23 mgKOH / g.

[0091] (3) A titanium catalyst was added in an amount as shown in Table 1, and vacuum polycondensation was carried out at 230-260° C. (vacuum degree ≤ 600 Pa) to react to a target viscosity to obtain a saturated polyester copolymer CP3.

[0092] Example 4

[0093] This example provides a saturated polyester copolymer, and the raw materials for preparation are as follows: 2-methylspiro[3.5]nonane-2,7-diol, 4,8-tricyclo[5.2.1.O2,7]decanedimethanol, 4,4'-dihydroxydicyclohexane, 2-methyl-1,3-propanediol, neopentyl glycol, hydroxyethylated bisphenol A, terephthalic acid, isophthalic acid, adipic acid, trimellitic anhydride and titanium catalyst. The specific amounts are shown in Table 1.

[0094] The preparation method of the saturated polyester copolymer of this example specifically comprises the following steps (the raw materials and amounts used in each step are shown in Table 1):

[0095] (1) In a reaction kettle equipped with a stirrer, a thermometer, a reflux condenser and nitrogen, the raw materials required for the first step reaction are added into the reactor according to the corresponding amounts shown in Table 1, including 2-methylspiro[3.5]nonane-2,7-diol, 4,8-tricyclo[5.2.1.02,7]decanedimethanol, 4,4'-dihydroxydicyclohexane, 2-methyl-1,3-propanediol, neopentyl glycol, hydroxyethylated bisphenol A, terephthalic acid, isophthalic acid, adipic acid, trimellitic anhydride and a titanium catalyst. Under a protective atmosphere of nitrogen, the temperature is gradually increased and kept at 220-240° C. for 4-6 hours, until the acid value of the system is reduced to below 18 mgKOH / g.

[0096] (2) Maintaining the reaction conditions of step (1), the raw materials required for the second step reaction, including 4,8-tricyclo[5.2.1.O2,7]decanedimethanol, isophthalic acid and adipic acid, were added in the corresponding amounts shown in Table 1, and the reaction was carried out until the acid value of the system was reduced to below 26 mgKOH / g.

[0097] (3) A titanium catalyst was added in an amount as shown in Table 1, and vacuum polycondensation was carried out at 230-260° C. (vacuum degree ≤ 600 Pa) to react to a target viscosity to obtain a saturated polyester copolymer CP4.

[0098] Comparative Example 1

[0099] This example provides a saturated polyester copolymer, and the raw materials for preparation are as follows: 2-methyl-1,3-propanediol, neopentyl glycol, hydroxyethylated bisphenol A, terephthalic acid, isophthalic acid, adipic acid and a tin catalyst. The specific amounts are shown in Table 1.

[0100] The preparation method of the saturated polyester copolymer of this example specifically comprises the following steps:

[0101] In a reactor equipped with a stirrer, a thermometer, a reflux condenser and nitrogen, the raw materials are added to the reactor in the corresponding amounts shown in Table 1, including 2-methyl-1,3-propanediol, neopentyl glycol, hydroxyethylated bisphenol A, terephthalic acid, isophthalic acid, adipic acid and a tin catalyst, and the temperature is gradually increased and kept at 230-250° C. for 6-7 hours under a protective atmosphere of nitrogen, until the acid value of the system is reduced to less than 25 mgKOH / g. Vacuum polycondensation (vacuum degree ≤ 700 Pa) is carried out to the target viscosity to obtain a saturated polyester copolymer CP5.

[0102] Comparative Example 2

[0103] This example provides a saturated polyester copolymer, and the raw materials for preparation are as follows: 2-methyl-1,3-propanediol, neopentyl glycol, hydroquinone dihydroxyethyl ether, trimellitic anhydride, terephthalic acid, isophthalic acid, adipic acid and a titanium catalyst. The specific amounts are shown in Table 1.

[0104] The preparation method of the saturated polyester copolymer of this example specifically comprises the following steps:

[0105] In a reactor equipped with a stirrer, a thermometer, a reflux condenser and nitrogen, the raw materials are added to the reactor according to the corresponding dosage shown in Table 1, including 2-methyl-1,3-propanediol, neopentyl glycol, hydroquinone dihydroxyethyl ether, trimellitic anhydride, terephthalic acid, isophthalic acid, adipic acid and titanium catalyst, and the temperature is gradually increased and kept at 230-250°C for 6-7 hours under the protective atmosphere of nitrogen, until the acid value of the system is reduced to less than 25 mgKOH / g. Vacuum polycondensation (vacuum degree ≤ 700 Pa) is carried out to the target viscosity to obtain a saturated polyester copolymer CP6.

[0106] Table 1 Raw materials and their amounts in each step of Examples 1 to 4 and Comparative Examples 1 to 2

[0107]

[0108]

[0109] The performance indicators of the saturated polyester copolymers prepared in Examples 1 to 4 and Comparative Examples 1 to 2 were tested, including acid value, hydroxyl value, number average molecular weight and glass transition temperature. The results are shown in Table 2.

[0110] Table 2 Performance indicators of saturated polyester copolymers of Examples 1 to 4 and Comparative Examples 1 to 2

[0111]

[0112] Application Examples 1 to 4 and Application Comparative Examples 1 to 2

[0113] An IMD ink is prepared by using the saturated polyester copolymers prepared in Examples 1 to 4 and Comparative Examples 1 to 2 as the main resin, and mixing with other raw materials to prepare the IMD inks of Application Examples 1 to 4 and Application Comparative Examples 1 to 2. The specific raw material composition is shown in Table 3.

[0114] Table 3 IMD ink raw material composition of application examples 1 to 4 and application comparative examples 1 to 2

[0115] Components Function Mass percentage Saturated polyester copolymers of Examples 1 to 4 and Comparative Examples 1 to 2 Main resin 38.0％ Duranate TKA-90SB Curing agent 3.0％ Takenate 500 Curing agent 0.8％ DBE Solvents 32.0％ Cyclohexanone Solvents 8.0％ Isophorone Thinner 7.0％ Carbon Black pigment 8.0％ TEGO 370 Leveling agent 0.2％ BYK 163 Dispersants 2.0％ DAVY DS P111 Accelerator 1.0％

[0116] The IMD ink prepared in the above-mentioned application examples 1 to 4 and the application comparison examples 1 to 2 was coated on the PC / PMMA / PET film by screen printing, and a curing ink coating was formed by heat treatment (50-80°C×1h). The adhesive was further printed and dried, and finally the IMD process was formed and injection molded to obtain an IMD plastic part. The performance of the ink coating on the film and the ink coating after the IMD process was tested. The test results are shown in Table 4.

[0117] Table 4 Performance of IMD inks of application examples 1 to 4 and application comparative examples 1 to 2

[0118]

[0119] As can be seen from Table 4, the IMD inks of Application Examples 1 to 4 of the present invention have good room temperature adhesion performance, and good heat resistance and stable adhesion performance. In contrast, the IMD inks of Comparative Examples 1 to 2 have poor room temperature adhesion performance, especially poor heat resistance and stable adhesion performance, and are difficult to meet the use requirements of the IMD process. It can be seen that the IMD ink coating prepared by using the saturated polyester copolymers of Examples 1 to 4 of the present invention can break through the technical bottleneck of the ink layer plastic substrate being difficult to adhere to and easy to fall off, significantly improve the stable adhesion performance of the coating in the IMD process, and further improve the comprehensive performance of the coating in terms of temperature resistance, tensile flexibility, adhesion, surface hardness, impact resistance, and low shrinkage.

Claims

1. A saturated polyester copolymer, characterized in that: The raw materials for preparing the saturated polyester copolymer include: compound a, compound b, compound c, polyol, catalyst; and also include polyacid and / or polyacid anhydride; The chemical formula of the compound a is shown in Formula 1: The chemical formula of the compound b is shown in Formula 2: The chemical formula of the compound c is shown in Formula 3: In Formula 1, each R1 is independently selected from a hydroxyl group, a carboxyl group or an amino group, and at least one R1 is a hydroxyl group; n1 ≥ 1 and n1 is an integer; In Formula 2, each R2 is independently selected from a hydroxyl group, a carboxyl group or an amino group, and at least one R2 is a hydroxyl group; each X is independently selected from a C1 to C10 alkyl group; 1≤n2≤5 and n2 is an integer; In Formula 3, each R3 is independently selected from a hydroxyl group, a carboxyl group or an amino group, and at least one R3 is a hydroxyl group; n3≥2 and n3 is an integer.

2. The saturated polyester copolymer according to claim 1, characterized in that In Formula 1, each R1 is independently selected from a hydroxyl group or an amino group, and at least one R1 is a hydroxyl group; and / or, in Formula 1, n1 is 1 to 10 and n1 is an integer; and / or, in Formula 2, each R2 is independently selected from hydroxyl or amino, and at least one R2 is hydroxyl; And / or, in Formula 2, 1≤n2≤3 and n2 is an integer; and / or, in Formula 3, each R3 is independently selected from hydroxyl or amino, and at least one R3 is hydroxyl; And / or, in Formula 3, n3 is 2 to 10 and n3 is an integer.

3. The saturated polyester copolymer according to claim 1, characterized in that The polyol includes a first polyol, or a combination of a first polyol and a second polyol; the first polyol includes a polyol containing a C6-C20 aromatic group and / or an ether group; the second polyol includes a C2-C20 fatty polyol, a C5-C20 alicyclic polyacid, or a combination thereof; and / or, the polyacid comprises at least one of a C6-C20 aromatic polyacid, a C2-C20 aliphatic polyacid or a C5-C20 alicyclic polyacid; and / or, the polyacid anhydride comprises at least one of a C6-C20 aromatic polyacid anhydride, a C2-C20 aliphatic polyacid anhydride or a C5-C20 alicyclic polyacid anhydride; And / or, the catalyst includes at least one of a tin-based catalyst, an antimony-based catalyst or a titanium-based catalyst.

4. The saturated polyester copolymer according to claim 3, characterized in that The first polyol includes hydroquinone dihydroxyethyl ether, hydroxyethylated bisphenol A or a combination thereof; and / or, the second polyol comprises at least one of neopentyl glycol, ethylene glycol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 1,4-cyclohexanedimethanol, hexadecanediol, trimethylolpropane or trimethylolethane; and / or, the polyacid comprises at least one of adipic acid, suberic acid, sebacic acid, dodecanedioic acid, cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid or trimellitic acid; And / or, the polyacid anhydride includes at least one of adipic anhydride, suberic anhydride, sebacic anhydride, dodecanedioic anhydride, cyclohexanedicarboxylic anhydride or trimellitic anhydride.

5. The saturated polyester copolymer according to any one of claims 1 to 4, characterized in that: The mass ratio of the compound a to the total amount of the raw materials for preparing the polyester copolymer is 0.5 to 40% by weight; And / or, the mass ratio of the compound b to the total amount of the raw materials for preparing the polyester copolymer is 0.5 to 60% by weight; And / or, the mass ratio of the compound c to the total amount of raw materials for preparing the polyester copolymer is 0.5-40%wt; And / or, the mass ratio of the compound b is greater than the mass ratio of the compound a; And / or, the mass proportion of the compound b is greater than the mass proportion of the compound c.

6. The saturated polyester copolymer according to any one of claims 1 to 4, characterized in that The ratio of the total molar amount of the compound a, compound b, compound c and polyol to the total molar amount of the polyacid and / or polyacid anhydride is (0.9-3.5):

1.

7. The saturated polyester copolymer according to any one of claims 1 to 4, characterized in that The number average molecular weight of the saturated polyester copolymer is 5 to 50 kDa; And / or, the glass transition temperature of the saturated polyester copolymer is -20 to 70°C; and / or, the acid value of the saturated polyester copolymer is 1 to 20 mgKOH / g; And / or, the hydroxyl value of the saturated polyester copolymer is 10 to 50 mgKOH / g.

8. A method for preparing a saturated polyester copolymer according to any one of claims 1 to 7, characterized in that: The following steps are involved: S1, mixing compound a, compound c, polyol, part of compound b, polyacid and / or polyacid anhydride, and catalyst, and performing a first polymerization reaction in a protective gas atmosphere to obtain a first polymer; S2, adding the remaining amount of compound b, polyacid and / or polyacid anhydride to the first polymer, and performing a second polymerization reaction in a protective gas atmosphere to obtain a second polymer; S3, adding the remaining amount of catalyst to the second polymer, and performing vacuum polycondensation reaction to obtain the saturated polyester copolymer.

9. The preparation method according to claim 8, characterized in that: The temperature of the first polymerization reaction is 200-260°C; and / or, the temperature of the second polymerization reaction is 200-260° C.; And / or, the temperature of the vacuum polycondensation reaction is 220-280°C; and / or, the reaction endpoint of the first polymerization reaction is that the acid value of the first polymer is ≤20 mgKOH / g; and / or, the reaction endpoint of the second polymerization reaction is that the acid value of the second polymer is ≤35 mgKOH / g; And / or, the vacuum degree of the vacuum polycondensation reaction is ≤600Pa.

10. An ink for in-mold injection molding decoration, characterized in that: The preparation raw materials include the saturated polyester copolymer described in any one of claims 1 to 7.

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